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Inorganic chemistry
Article in Annual Reports on the Progress of Chemistry · January 1966

DOI: 10.1039/AR9666300129
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INORGANIC CHEMISTRY
1. INTRODUCTION
By E. A. V . Ebsworth
( University Chemical Laboratory, Cambridge)
J. Lewis
(The ‘victoria University of Manchester)
THEgeneral form of the Annual Reports is essentially the same as last year,
except for the addition of a section on kinetics of inorganic reactions. Per-
haps the most important development in the field of inorganic chemistry
has been the isolation of complexes of nitrogen with ruthenium and
iridium, and the conversion of nitrogen into ammonia by transition-metal
complexes.s This will obviously provide an impetus for considerable effort
in this field of chemistry over the next few years.
As noted last year, the rate of publication of Papers continues to in-
crease, and hence the coverage of the literature in a report of this type
becomes more subjective. A number of review journals have appeared to
help in the assimilation of this large flow of Papers, and it is t o be hoped that
these reviews will involve the comprehensive as well as the more general
review articles. Among the new series which appeared this year are
Tramition Metal Chmistry, vol. 1--III,4 Structure and Bonding,S Organo-
metallic Chemistry Reviews,6 and Co-ordination Chemistry Reviews.7 A n
additional communication journal, Inorganic and Nuclear Chemistry Letters,8
the first number of which is dated October 1965, and the second volume
of Phillips and Williams’s book on ‘‘ Inorganic Chemistry ” have also been
published.
A. D. Allen and C. V. Senoff, Chem. Comm., 1966, 621.
a J. P. Collman and J. W. Kang, J . Amer. Chern. Xoc., 1966,88, 3459.
M. E. Vol’pin and V. B. Shur, Nature, 1966, 209, 1236.
Transition Metal Chemistry, ed. R. L . Carlin, Arnold, London, 1966.
Structure and Bonding, Springer, New York, 1966.
(I Organmetallic Chemistry Reviews, Elsevier, Amsterdam.
Coordination Chemistry Reviews, ed. A. B. P. Lever, Elsevier, Amsterdam.

a Inorganic and Nuclear Chemistry Letters, Pergamon Press, New York.
O C. S. G. Phillips and R. J. P. Williams, “ Inorganic Chemistry,” vol. 11, Clarendon
Press, Oxford, 1966.
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2. KINETICS AND MECHANISMS OF INORGANIC REACTIONS

By J. Burgess
(ChemistryDepartment, Leicester University)
As is usual in these Reports it is only possible to mention a proportion,

here about a quarter, of the year's relevant references. In the process of
selection all references to two active fields which overlap organic chemistry,
organo-silicon and -germanium chemistry, and oxidations of organic com-
pounds by inorganic species, have been eliminated. The emphasis on
reactions of transition-metal complexes in this Report reflects the continued
major interest in this aspect of inorganic kinetics. [Throughout this Report
L stands for any ligand, as specified in the text, X stands for a halogen atom
((31, Br, I) unless otherwise stated, and AH$ and A$ represent enthalpies
and entropies of activation. References to the Russian literature quote
page numbers of the English translations.]
Redox Reactions.-There has again been much work on inner-sphere
reductions of cobalt(m) Complexes by chromium(@. cis-[Co(en),(N,),]+ and
cis-[Co(NHC,),(N,),]+ react by parallel paths involving a single or a double
azide bridge.l For [Co(en>,(NCS)Xln+ (X = C1, NCS, NH,, OH,) chrom-
ium@) attack can occur a t either nitrogen or sulphur to form the thiocyanate
bridge., The importance of steric factors and ligand reducibility have been
investigated for reduction of thirty carboxylatopenta-amminecobalt(m)
complexes; for aromatic carboxylate ligands containing anitro group there
is evidence for chromium(n) attack a t the nitro group.3 The rate of ring
closure of [Cr(OH2),(O,C*CH,*CO,H)],+, containing unidentate malonate, to
the chelate [Cr(OH2),(O,C*CH,*CO,)]+ is much slower than the rate of reduc-
tion of [Co(NH,),( 02C*CH2*C02H)]2+by chromium(n).4 This evidence,
together with rate constants and product distribution from analogous reduc-
tions of malonate half-ester c~mplexes,~ refutes the earlier postulate of
chromium(@ attack a t the remote oxygen atom of the malonate ligand.
The transition state now suggested contains chromium bonded to oxygen
atoms from both carboxyl groups of the bridging malonate. The nature of
intermediates in the chromium(11) reduction of nicotinamido- and isonicotin-
amido-penta-amminecobalt(m) casts further doubt on the general applica-
bility of the remote attack hypothesis.6 Reaction rates of chromium(I1)with
cis- and truns-[Co(en),(OH2),]3+and [Co(en),(OH2)(NH,)33findicate a trans
effect, though this is much less marked than for reduction by iron(=).'
Electron exchange in the chromium(lr)-[Cr(OH2),(NH,)I3+ reaction
occurs by an inner-sphere mechanism.8 The detection of transient iron(m)
* A. Haim, J. Amer. Chem. SOC.,1966, 88, 2324.
a A. Haim and N. Sutin, J . Arner. Chem. Soc., 1966, 88,434.
E. S. Gould, J . Amer. Chem. SOC.,1966, 88, 2983.
D. €I. Huchital and H. Taube, Inorg. Chem., 1965, 4, 1660.
D. H. Huchital and H. Taube, J . Amer. Chem. Soc., 1965, 87, 5371.
6 F. R. Nordmeyer and H. Taube, J. Amer. Chem. SOC., 1966, 88, 4295.
7 R. D. Cannon and J. E. Earley, J . Amer. Chem.Soc., 1965,87,5264; 1966,88,1872.
* J. H. Espenson and D. W. Carlyle, Inorg. Chem., 1966, 5,586.
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BURGESS : KINETICS O F I N O R G A N I C REACTIONS 131
complexes by fast reaction techniques in the reaction of iron(=) with several
cobalt@) complexes confirms that these are also inner-sphere reaction^.^
Transition-state chromium-oxygen-vanadium bridging has now been demon-
stratedl0 and may be compared with earlier reports of Cr-O-Cr and V-0-V
bridging. V-0-U bridging occurs in the vanadium(m)-uranium(vr) re-
action.ll
The use of the “oxygen isotopic fractionation factor,” f, the ratio of
rates, d In lS0/d In l*O, has been discussed as a means for differentiating
between inner-sphere and outer-sphere oxidations. For inner-sphere oxida-
tions, e.g. [Co(NH3),(OH)]2+-chromium(rr), where Co-0 bond stretching is
important in the formation of the transition state, f is significantly larger
than for outer-sphere oxidations, e.g. [CO(NH~),(OH)]~+-[RU(~H,),]~
Vanadium(r1)and europium(rr)reductions have f values similar to those for
[Ru(NH,),]~+reductions, suggesting that these cations, unlike chromium(n),
reduce penta-amminecobalt(m)complexes by an outer-sphere mechanism.12
However, there is evidence for chlorine bridging in the europium(rr)-
chromium(m) system.l3
There have been several studies of outer-sphere redox reactions. Rates
and activation parameters have been determined by the temperature-jump
technique for the hexachloroiridate(n)-hexabromoiridate(m)forward and
reverse reactions.l4 Electron transfer rates in the manganate-perruthenate
system have been reported ; in the ruthenate-perruthenate system rates
were too fast to follow. These results were compared with rnanganate-
permanganate electron exchange data in the light of Marcus’s theories.15
l[ron(m) oxidation of [Ta6CIl,]2+ to [Ta,C1,2]4+proceeds by two one-electron
transfers.16 Electron transfer in the system iron(=)-iron(m) in complexes
with 1,lO-phenanthroline (unsubstituted and methyl derivatives) is too fast
to measure even from n.m.r. line-broadening.l7 Rates of oxidation of
ruthenium@) complexes of substituted 1,lo-phenanthrolines by cerium(rv)
are consistent with Marcus’s equations for outer-sphere oxidations.l*
Activation energies and frequency factors for oxidation of the same com-
plexes by t h a l l i u m ( ~ n )and
, ~ ~of iron(@ Complexes of the same ligands by
peroxodisulphate,*O show linear correlation over a wide range of values.
The question of one- or two-electron transfers in redox reactions involving
thallium has been discussed in several other papers. In the silver(n-
thallium(1) reaction in nitric acid, two one-electron steps are indicated ;21
similarly, results of vanadium(m)-thallium( III) experiments rule out simul-
A. Haim and N. Sutin, J . Amer. Chem. SOC.,1966, 88, 5343.

lo J. H. Espenson, Inorg. Chem., 1965, 4, 1533.
T. W. Newton and F. B. Baker, J . Phys. C‘hem., 1966, 70, 1943.
l3 H. Diebler, I?. H. Dodel, and H. Taube, Inorg. Clzern., 1966, 5, 1685.
l3 A. Adin and A. G. Sykcs, J . Chem. SOC. (A), 1966, 1230.
P. Hurwitz and K. Kustin, Trans. Paraday SOC.,1966, 62, 427.
l 5 E. V. Luoma and C. H. Brubacker, Inorg. Chena., 1966, 5, 1618, 1637.
l6 J. H. Espenson and R. E. McCarley, J . Amer. Chern. Xoc., 1966, 88, 1053.
l 7 D. W. Larsen and A. C. Wahl, J. Chem. Phys., 1965, 43, 3765.
l8 J. D. Miller and R. H. Prince, J . Chem. SOC. (A), 1966, 1370.
J. D. Miller and R . H. Prince, J . Chem. SOC.(A), 1966, 1048.
8 o J. Burgess and R. H. Frince, J . Chem. SOC. (A), 1966, 1772.
21 R. ‘VV.Dundon and J. W. Gryder, Inorg. Chern., 1863, 5,986.
View Article Online
132 INORGANIC CHEMISTRY
taneous two-electron transfer.22 However, kinetics of the vanadium(@-

t U u r n ( m ) reaction, and relative rates of reaction of vanadium(rr) and
vanadium(rn) with thallium(m), suggest two-electron transfer in this
case.23
The importance of ion-pairing in redox reactions has been illustrated for
reaction of ferrocyanide with peroxodisulphate, where variation of rate with
potassium ion concentration indicates that [KFe(CN),]3- and [KS,O,]- are
the reacting species.24
Substitution Reactions of Complexes.-The temperature-jump method
has proved valuable for studying kinetics of formation of complexes.
Iron(rr) reacts with nitric oxide a t approximately the same rate as with
lJ0-phenanthroline or 2,2’-bipyridyl.25 I n formation of a-alanine com-
plexes of nickel(=) and cobalt(@ the rate-determining step is the loss of a
water molecule, but the kinetics of formation of the manganese(n) complex
with B-alanine are consistent with rate-controlling ring closure.a6 Tempera-
ture-jump 27 and pressure-jump 28 studies of the reaction of nickel(=) with
malonate give similar results; the rate-determining step is the loss of water
from the nickel cation followed by reaction with malonate or hydrogen
malonate ion. This mechanism is the same as for the cobalt(@-malonate
reaction.29 Temperature-jump studies of the reaction of magnesium(n)
with oxine also indicate parallel reactions of the metal ion with ligand and
with protonated ligand.30
+
The equilibrium Co3+ C1- + CoC12+ in hydrochloric acid has been
investigated by the stopped-flow method.s1 The forward reaction is inter-
esting as a rare example of a reaction of aquated cobalt(m). Formation of
the mono-acetylacetone (acac) complex of iron(m) in acid solution 3 2 occurs,
as in the malonate and oxine examples above, by parallel reactions of acac
and acac.€€+ with FeSf or with Fe(OH)2+. But kinetics of reaction of
copper(=) with acetylacetone indicate reaction only with the unprotonated
ligand.s3 Rates of formation of terpyridyl complexes of first-row transition
metals are similar to rates of formation of the respective 1,lO-phenanthroline,
2,2’-bipyridyl, and pyridine complexes, which implies that attachment of
the first nitrogen is the kinetically important stage for each of these ligands.
The stability constants of the monoterpyridyl complexes are dictated by
rates of dissociation rather than of formation.34 Replacement of water
molecules by diethylenetriamine (as dien.H+) or nitrilotriacetate (N’I’AS-)
z2 N. A. Daugherty, J. Amer. Chem. SOC.,1965, 87, 5026.
2s F. B. Baker, w. D. Brewer, and T.W. Newton, I n o r g . Chem., 1966, 5, 1294.
84 R.W. Chlebek and M. W. Lister, Cunud. J. Chem., 1966, 44, 437.
2 5 K. Kusth, I. A. Taub, and E. Weinstock, I n o r g . Chem., 1966, 5, 1079.
26 K. Kusth, R. F. Pasternak, and E. M. Weinstock, J . Amer. Chem. SOC., 1966,
88, 4610.
27 F. P. Cavasino, J . Phys. Chem., 1965, 69, 4380.
2 8 H. Hoffman and J. Stuehr, J . Phys. Chem., 1966, 70, 955.
2 8 F. p. Cavasho, RiceTCa S C ~ . , 1965, 8A, 1120.
5 0 D. N. Hague and M. Eigen, Trans. Paraday soc., 1966, 62, 1236.
31 T.J. Conocchioli, G. H. Nancollas, and N. Sutin, I n o r g . Chem., 1966, 5, 1.
8 2 W. K. Ong and R.H. Prince, J . Chem. SOC. ( A ) ,1966, 458.
33 R. c. &rile, M. Cefola, P. 8. Gentile, and A. V. Celiano, J . Phys. Chem., 1966,
70, 1358.
a4 R. H. Holyer, C. D. Hubbard, S . F. A. Kettle, and R. G. Wilkins, InoTg. Chem.,
1966, 5, 622.
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B U R G E S S : K I N E T I C S O F I N O R G A N I C REACTIONS 133
in [Ni(0H2),L]2+ (L = substituted 1,lO-phenanthroline) occurs a t rates
whose logarithms correlate with Hammett Q constants for the respective
substituents. This shows effective transmission of substituent effects across
both ligand molecule and metal atom t o the reaction site. The difference
in electrostatic interaction accounts for the very much faster reaction of
[Ni(OH2),L]2+ with NTA3- than with dien. H+.35
The unwrapping of a multidentate ligand from one metal ion and its
transfer to another has been studied for copper(n)-EDTA reacting with
nickel(=) and zinc(=) tetraethylenepentamine complexes,36with zinc(=) in
the presence of hydroxide, acetate, and azide ions,S7and for cobalt(n)-EDTA
with nickel@).38 Dissociation of complexes of EDTA derivatives has also
been studied, €or instance mercury(rr)-trans-1,2-diaminocyclohexanetetra-
acetate in acid solution;3Qalso cobalt@)-EDTA and cobalt(m)-hydroxy-
ethylethylenediaminetriacetate in acid solution 4 O and in the presence of
thaUium(m).41 The mechanism of EDTA exchange in solutions of its
calcium complex involves several paths, the relative importance of which
depends strongly on pH.d2 Ligand exchange reactions for tetra-ligand
complexes of zirconium, hafnium, and thorium with acetylacetone and
trifluoroacetylacetone have been investigated by n.m .r. spectros~opy.~~
The dependence of racemisation rates of [Cr(02C-C02)3]3-on the nature
of the complementary alkali metal cation in solution suggests an inter-
mediate in which an oxalate is bonded by only one oxygen to the chromium.44
Hydrolysis rates of [Ni(aca~),],~~ and of [VO(acac),] and [ B e ( a c a ~ ) ~at] , ~ ~
varying acid concentration, imply that protonation of unidentate acetyl-
acetone molecules is an important factor in the mechanism, but kinetics of
aquation and lSO exchange for [Cr(acac),] show no evidence for a significant
contribution from protonation of unidentate ligand molecules.47
There is still much work on reactions of complexes of the penta-
amrninecobalt(n1) type. Gay and Lalor 48 were not able to distinguish
between 8,lC.B and SN2P mechanisms for hydroxide reaction with
[Co(NH3),(NCS)]2+or [Cr(NH,),(NCS)J2+,but Banerjea and das Gupta 4Q
favour the &2IP mechanism for base hydrolysis of the former. For re-
actions of [Co(en),LX]"+ (L= OH, NO2, Cl, or an amine; en = ethylene-
diamine or one of its substituted derivatives) kinetics of reactions under
various conditions, deuterium isotope effects, and steric effects all indicate
R. K. Steinhaus and D. W. Margerum, J. A m y . Chern. SOC.,1966, 88, 441.
85
D. W. Margerum and J. D. Carr, J . Amer. Chem. SOC.,1966, 88, 1639, 1645.
36
37 D. W. Margerum, B. A. Zabin, and D. L. Janes, I n o r g . Chem., 1966, 5, 250.
38 T. R. Bhat, D. Radhamma, and J. Shankar, Inorg. Chem., 1966, 5, 1132.
38 D. 1;. Janes and D. W. Margerum, Inorg. Chem., 1966, 5, 1135.
4 0 S. P. Tanner and W. C. E. Higginson, J. Chem. SOC. ( A ) ,1966, 537.
41 S. P. Tanner and W. C. E. Higginson, J. Chem. SOC. ( A ) ,1966, 59.
4 2 R. J. Kula and G. H. Reed, Analyt. Chem., 1966, 38, 697.
4 3 A. C. Adams and E. M. Larsen, I n o r g . Chem., 1966, 5, 228, 814; T. J. Pinnavaia
and R.C. Fay, ibid., p. 233.
4 4 J. A. Kernohan, A. L. Odell, R. W. Olliff, and F. B. Seaton, Nutwe, 1966, 209,
906.
45 R . G. Pearson and J. W. Moore, Inorg. Chem., 1966, 5, 1523.
R. G. Pearson and J. W. Moore, Inorg. Chem., 1966, 5, 1528.
4 7 J. Agett and A. L. Odell, J. Chem. SOC.( A ) ,1966, 1820.
4 6 D. L. Gay and G. C. Lalor, J. Chern. SOC.( A ) ,1966, 1179.
4 Q D. Banerjea and T. P. das Gupta, J. InoTg. Nuclear Chem., 1966, 28. 1667.
View Article Online
&11P or &21P mechanisms, never XNlCB.50 Ion-pairing has a marked

effect on the rate of aquation of [Cr(NH,),Cll2+ in the presence of sulphate,
nitrate, or several organic anions; faster rates in the presence of these ions
are ascribed to enhanced reactivity of ion-~airs.5~ Kinetics and products of

base hydrolysis of [CO(NH,),X]~+ (X = C1, Br, I, NO,) in solutions contain-
ing added ions, e.g., NCS-, SO4,-, can be explained much more
readily by an SNICBthan by an 5 2, but kinetics of cyanide
exchange with [Co(en),(SO,)(CN)]seem inconsistent with an SNlcB mech-
a n i ~ r n .Kinetic
~~ studies of this type in non-aqueous solvents are yielding
results but it is still too early to draw definite conclusion^.^^
Both cis- and trans-[Co(en),(NO,) (NCS)]+ and [Co(en),(NO,) (NH9)I2 +, in
acid solution, aquate by an SN1C.A mechanism rather than the SN2CA
mechanism more usually found for cobalt(m), rhodium(rn), and iridium(m)
complexes of this type.55 Several other examples of the importance of
protonation of nitro groups in acid aquation have been reported, for the
[Co(NR,),(NO,)] +, [Co(NH,),(NO,),] +, and [Co (en),(NO,),] + cations.56
,
Reactions of [Co (NH,) (OH,)] + and [Co(en) (OH,) ,] + with cyanate have
been studied by tracer experiments. The product carbamato-complex is
formed from the former without breaking the cobalt-oxygen bond, and in
the [Co(en),(CO,)]+ from the latter the carbonato ligand contains one oxygen
atom from the water originally on the cobalt, one from the cyanate, and
one from the solvent.67
Rates of halogen exchange for [Rh(NH3),XI2+and [:Ir(NH3)5X]2+ are
in the same order as rates for the analogous halogenopenta-amminecobalt(m)
complexes 58 and parallel ligand-field strengths, but reaction rates of
[Rh(NH3),XI2+with hydroxide are in the opposite order.59 A significant
trans effect, both on rates and on actimtion energies, has been reported
for trans-[Rh(en),X,]+ reacting with various X-. Results imply a wide
..
variation in the importance of Rh . OH2 bonding in the transition states
for different pairs of halogens as X and Reaction of [Rh(OH,)J3+
with chloride involves the initial rate-determining loss of one water molecule ;
the marked inverse dependence of rate on pH is due to the greater reactivity
of [Rh(OH2),(0E)]2+than of the hexa-squo ion.61
Further examples of square-planar complexes which exhibit kinetic
behaviour characteristic of octahedral complexes have been reported. In
So S. C . Chan and F. Leh, J . Chem. SOC. ( A ) ,1966, 126, 129, 134, 138; S. C. man,
ibid., pp. 142, 1124, 1310.
61 J. B. Walker and C. B. Monk, J . Chem. SOC.( A ) ,1966, 1372.
6 2 D. A. Buckingham, I. I. Olsen, and A. M. Sargeson, J . Amer. Chem. SOC., 1966,
88,5443.
53 E. Campi, C. Paradisi, G . Schiavon, and M. L. Tobe, Chem. Comm., 1966, 682.
6 4 E.g., B. Bosnich, J. Ferguson, and M. L. Tobe, J. Chem. SOC. ( A ) ,1966, 1636.
5 5 R. V. Bradley, E. 0. Greaves, and P. J. Staples, J . Chem. SOC. ( A ) ,1966, 986.
( A ) ,1966, 1; D. G. Lambed and J. G. Meson, J. Amer.
6 8 G. C. Lalor, J . Chem. SOC.
Chem. SOC.,1966, 88, 1633, 1637; U. D. Gomwalk and A. McAuley, J . Chem. SOC.( A ) ,
1966, 1692, 1694.
5 7 A. M. Sargeson and €3. Taube, Inorg. Chem., 1966, 5, 1094.
6 8 G. B. Scmidt, 2.phys. Chem. (Frankfurt), 1966, 50, 222.
5 9 0. W. Bushnell, G. C. Lalor, and E. A. Moelqm-Hughes, J . Chem. SOC.( A ) ,
1966, 719.
6 0 H. L. Bott, E.J. Bounsall, and A . J. Poci, J . Chem. Soc. ( A ) , 1966, 1275.
61 K. Swaminathan and G. M. Harrsi, J . Amer. Chem. SOC.,1966, 88, 4411.
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BURGESS : K I N E T I C S O F INORGANIC REACTIONS 135
palladium(=) complexes of N-alkyltriamines bulky alkyl groups lead to such
“pseudo-octahedral ” behaviour. Hydroxide ion catalysis has been demon-
strated for these complexes and explained by a CB mechanism; this is the
f i s t example of hydroxide catalysis in a square-planar system.62 Pseudo-

octahedral behaviour is also found 63 in reactions of the gold(m) complex
[AU(l?h4dien-H)X](PF6), where Et,dien-H represents the anion formed by
removal of a proton from tetraethyldiethylenetriamine, but the species
[Au(dien)ClI2+,which lacks the sterically-interfering ethyl groups, exhibits
normal square-planar kinetic behaviour. The normal rate law also applies
to reactions of [AuC13L] (L = heterocyclic nitrogen base) with chloride,
azide, and nitrite,64 and to the reverse reaction of [AuClJ- with L.65The
[AuCl,L] reactions exhibit marked nucleophilic discrimination, and second-
order rate constants depend greatly on the nature of the substrate and
entering group. Rate constants for reaction with chloride are linearly related
to the basicity of the leaving group. Rate constants for reaction of
[Pt(bipy)Cl,] ~ t aliphatic
h amines and pyridines are linearly related to the
basicity of tbe entering group,66though basicity plays a smaller role in deter-
mining reactivity in platinum(@ than in gold@) complexes. Rate con-
stants, and so,meA H $ and AS$ values, have been reported for many reactions
of [PtL,X,] (L = nitrogen or phosphorus base). Complexes where L = PEt,
have proved especially useful as they shorn high nucleophilic discrimination.
Results are discussed in terms of ligand polarisabilities and solvation
effects.67 Although the rate law for hydroxide reaction with trans-
pt(H2N*CH,~CH2*OB),C1,] takes the form normal for square-planar species,
direct attack of hydroxide at platinum seems less likely than an anchimeric
assistance mechanism.6g Isomerisationrates for [Pd(NCS)L]+ +[Pd(SCN)L]+
[L = (Et,N*CH,*CH,),NH], and reaction rates for both isomers with brom-
ide, indicate that this isomerisation is inter- rather than intra-molecular.6*
The trans effect in palladium@) complexes has been studied for carbon
monoxide reaction with [PdX,IZ- (X = halide, NO,, NCS, CN). These
and earlier resnlts lead to the same trans effect series as established for
platinum(@ Kinetics of cleavage of halogen-bridged platinum(n) com-
plexes by amines have been compared with those of amine attack on normal
unbridged platinum(n) complexes.71
Ca,rbonyls.-Kinetics of carbon monoxide exchange, and of triphenyl-
phosphine reaction, with nickel carbonyl are fist-order in carbonyl and zero-
order in CO or PPh,, and the reactions occur a t similar rates in toluene
62 W. H. Baddley and F. Basolo, J. Amer. Chem. SOC.,1966, 88, 2944.
63 C. F. Weick and F. Basolo, Inorg. Chem., 1966, 5, 576.
64 L. Cattalini and M. L. Tobe, Inorg. Chem., 1966, 5, 1145.
6 5 L. Cattalini, M. Nicolini, and A. Orio, Inorg. Chem., 1966, 5, 1674.
6 6 L. Cattalini, A. Orio, and A. Doni, Inorg. Chem., 1966, 5, 1517.
6 7 G. Faraone, U. BeUuco, V. Ricevuto, and R. Ettorre, J . Inorg. Nuclear Chem.,
1966, 28, 863; U. Belluco, A. Orio, and M. Martelli, Inorg. Chenz., 1966, 5, 1370, and
references therein.
6 8 F. Basolo and K. H. Stephen, Inorg. Nuclear Chem. Letters, 1966, 2, 23.
F. Basolo, W. H. Baddley, end K. J. Weidenbaum, J . Amer. Chem.SOC.,1966.
88, 1576.
7 O A. B. Fasman, G. G. Kutyukov, and D. V. Sokol’skii, Russ. J . Inorg. Chem.,
1965, 10, 727.
7l R. G . Pearson and M. M. Muir, J . Amer. Chem.SOC., 1966, 88, 2163.
View Article Online
136 I N O R G A N I C CHEMISTRY
at 0"c. It was therefore assumed that these reactions had a common rate-
determining step, the loss of a molecule of CO from the carbonyl. Enthlpies
and entropies of activation €or the two reactions have now been shown to
differ greatly, implying more complicated mechanisms.72 Results have also

been publishedfor similarreactions of Hg[Co(CO),], and related c0mpounds.7~
Werner and Prinz v4 found reactions of molybdenum hexacarbonyl with
benzene derivatives, amines, and phosphines to be first-order in carbonyl
and zero-order in base, although rates did depend on the nature of the
entering base. Angelici and Graham,75working a t higher base concentra-
tions, showed that the full rate-law was: rate = E,[Mo(CO),]+E,[Mo(CO),]
[base]. The second-order term represents Sx2 attack by the base, but
whether at molybdenum or carbon is not known. In compounds
Mo(CO),L, (L = toluene, p-xylene, mesitylene) replacement of L by PCl,,
PPhCl,, or P(n-C4Hg)3follows simple second-order kinetics.76
Reaction of Co(CO),(NO) with phosphines, arsines, or nitrogen bases itJ
second-order, in contrast to analogous reactions of isoelectronic Ni(Co),.'?
There is a similar difference in kinetic behaviour between reactions of the
isoelectronic compounds Co(CO),(NO)Land Ni(CO),L [L= Asph,,P(OR),,
Decomposition of cobalt hydrogen carbonyl is a simpl~second-order
rea~tion.'~Replacement of carbon monoxide in n-cyclopentadienylrhodium
dicarbonyl by phosphine, phosphites, and isonitriles is also second-order.m
Addition of water, oxygen, or methyl iodide to trans-[Ir(CO)(PPh,),X] is
again second-order;the activation parameters give some clues to the natures
of the transition states.81
Typical Elements.-Decompositions of nonaborane-15 and octaborane-12
are first-order.82 Reactions of the type PhBC1, plus 2,4-dinifronaphthyl-
amine show second-order kinetics and are thought to occur by an SN2
mechanism.83 The mechanism of decomposition 84 of BH,,PF, and similar
adducts is similar to that of BIE,,CO, that is BH,,L +BH, +
L followed
+ +
by BH, BH,,L ---f B2H6 L. Alkaline hydrolysis of BF,,ONMe,, ~ E I
of BF,,amine adducts, is first-order, independent of hydroxide concentra-
tion ; a 5 alkaline hydrolysis of SO,,NEt, is second-order, which is consistent
with nucleophilic attack by OH- a t sulphur.86 Kinetics of hydroxide
reaction with difluoramine, HNF,, are also second-order; the mechanism
L. R. Kangas, R. F. Heck, P. M. Henry, S. Breitschaft, E. M. Thorsteinson, and
F. Basolo, J. Amer. Chem. SOC., 1966, 88, 2334.
7 8 S. Breitschaft and B. Basolo, J . Amer. Chem. SOC., 1966, 88, 2702.
7 4 H. Werner and R. Prinz, J . Organometallic Chem., 1966, 5, 79; H. Werner, ibid.,
p. 100.
7 5 R. J. Angelici and J. R. Graham, J. Amer. Chem. SOC., 1966, 88, 3658.
7 6 F. Zingales, A. Chiesa, and F. Basolo, J . Amer. Chem. SOC., 1966, 88, 2707.
7 7 R. J. Mawby, D. Morris, E. M. Thorsteinson, and F. Basolo, Inorg. Chem., 1966,
5, 27; E. M. Thorsteinson and F. Basolo, J. Amer. Chem. SOC.,1966, 88, 3929.
7 8 E. M. Thorsteinson and F. Basolo, I m r g . Chem., 1966, 5, 1691.
7s K. H. Brandes and H. B. Jonassen, 2. anorg. Chem., 1966, 343, 215.
H. G. Schuster-Woldan and F. Basolo, J . Amer. Chem. SOC.,1966, 88, 1657.
81 P. B. Chock and J. Halpern, J. Amer. C h m . SOC., 1966, 88, 3511.
8 2 J. F. Ditter, J. R. Spielman, and R. E. Williams, Inorg. Chem., 1966, 5, 118.
J. C. Lockhart, J. Chem. SOC.( A ) ,1966, 809.
84 A. B. Burg and Yuan-Chin Fu, J. Amer. Chem. SOC., 1966, 88, 1147.
8s I. G. Ryss and S. L. Idel's, Rust?.J . Inorg. Chem., 1966, 10, 424.
8 6 I. G. Ryss and L. P. Bogdanova, Rws. J . Inorg. Chem., 1965,lO. 91.
View Article Online
BURGESS : K I N E T I C S O F INORGANIC REACTIONS 137
may be SN2, as for NF,, or assisted XN1, but does not involve ionisation of
HNF2.s7 Rates of racemisation and deuteriation of the complex cation
[Co(NH3),(CH3*NH-CH,.C0,)12'suggest retention of configuration about
the sarcosine-N atom for a kinetically significant, time after loss of the
proton.
Cleavage of Sn-Sn bonds in hexaphenylditin has been investigated by
reaction with iodine. The second-order kinetics, e.s.r., and DPPH reaction
experiments give no evidence for a significant contribution from radical
reacti0ns.8~ Nor is there any evidence for the generation of radicals during
the iodination of several other ditin compounds in a variety of
except from hexamethylditin under the most favourable condition^.^^ Pre-
equilibrium with solvent followed by formation of an acyclic four-centre
transition state seems the more usual mechani~rn.~~ Tin-phenyl bond
cleavage in the reaction of Ph2SnC1, with oxine takes place both by simple
bond breaking and by formation and decomposition of an adduct
Ph,SnCl,,(~xine),.~~ The mechanism of reaction of tetra-alkyl lead com-
pounds with iodine is SE2 substitution a t carbon; results in a variety of
solvents indicate significant solvation in the transition state.93
Anions.-Kinetics of hydrolysis of pyropho~phite,9~ pyrophosphate~,~~
and peroxopho~phates,~~ of alcoholysis of polyphosphoric acidsYg7 and of
reaction of peroxo-di-phosphate with iodine have been reported.gs In all
cases the variation of concentrations of variously protonated species a t
different pH values makes deduction of complete reaction mechanisms
hazardous if not impossible. Similar difficulties are encountered in halide-
halate reactions, e.g., iodide-cWorite.99 The most informative work has
been the investigation of base hydrolysis of the dichromate ion by water,
ammonia, hydroxide ion, and 2,6-lutidine.lo0 The order of reactivity
parallels basicity if due allowance is made for electrostatic repulsion and
for steric effects in the cases of hydroxide and lutidine, respectively. The
behaviour of Cr,0,2- is very similar to that of S,0,2-
A. D. Craig and G. A. Ward, J. Amer. Chem. SOC.,1966, 88, 4526.
88 B.Halpern, A. M. Sargeson, and K. R . Turnbull, J. Amer. Chem. SOC.,1966, 88,
4630.
D. N. Hague and R . H. Prince, J. Inorg. Nuclear Chem., 1966, 28, 1039.
O0 G. Tagliavini, S. Faleschini, G. Pilloni, and G. Plazzogna, J. OrganometaUk
Chem., 1966, 5, 136.
91 H. C. Clark, J. D. Cotton, and J. H. Tsai, Canad. J. Chem., 1966, 44, 903.
O S D. F. Martin and R. D. Walton, J. OrganometaUic Chem., 1966, 5, 57.
O S L. Riccoboni, G. Pilloni, G. Plazzogna, and G. Tagliavini, J . ElectroanaZyt.Chem.
Interfacial Electrochem., 1966, 11, 340.
O 4 R. E. Mesmer and R . L. Carroll, J . Amer. Chem. SOC., 1966, 88, 1381.
O 5 R. P. Mitra, H. C. Malhotra, and D. V. S. Jain, Trans. Faraday SOC., 1966, 62,
173; C. A. Bunton and H. Chaimovich, Inorg. Chem., 1965, 4, 1763.
O 6 S. H. Goh, R. B. Heslop, and J. W. Lethbridge, J. Chem. SOC. ( A ) ,1966, 1302.
9 7 F. B. Clarke and J. W. Lyons, J. Amer. Chem. Soc., 1966, 88, 4401.
9 8 A. Indelli and P. L. Bonora, J. Amer. Chem. SOC.,1966, 88, 924.
9 9 J. de Meeus and J. SigalIa, J. Chim. phys., 1966, 63, 453.
looP. Moore, S. F . A. Kettle, and R. G . Wilkins, Inorg. Chern., 1966, 5, 220.
View Article Online
3. THE TYPICAL ELEMENTS,

By A. J. Downs
(Inorganic Chenzistry Laboratory, South Park8 Road, Oxford)
E. A. V. Ebsworth and J. J. Turner
( Univer&ty Chemical Laboratory, Lensfceld Road,Cambridge)
INthe past year there has been no particularly important advance in the
chemistry of the typical elements. A series of papers deals with the electro-
chemistry of organometallic compounds and the electrochemicalformation of
metal-metal b0nds.l Other work implies that two commonly used methods
of assessing the strengths of donor-acceptor bonds are of doubtful validity :
manometric investigations of some sulphide adducts do not support a scale
of donor strengths based on adduct volatility;2athe variations in the (CkO)
stretching frequency of perinaphthenone accompanyingreaction with various
acceptors are not directly related to the formation constants of the com-
plexes.2b For adducts of several Lewis acids, the relative strengths of bases
appear to depend principally on the strength of the acid, and not neces-
sarily on supplementary rc-bonding.2c The concept of the donor number has
been introduced into discussions of non-aqueous solvents.2d
Reviews have been published on the following topics : the structures and
reactions of carbanionic organometallic compounds 3a of the elements of
Groups I-VI ; the preparation of methylmetal compounds using fused
salts ;3b the preparation and properties of pentafluorophenyl compounds of
main group and transition elements;3c organometnllic azides ;3d inorganic
analogues of carbenes;3* five co-ordination;3t the n.m.r. spectra of organo-
metallic compounds.39 A monograph dealing with the hydrogen compounds
of the metallic elements 40 has appeared; a collection of articles about non-
aqueous solvent systems has been p~blished,~b and a substantial study of
inorganic and general chemistry in liquid ammonia4crepresents Part I of
Volume I of a series. A collection of data relating to the appearance poten-
(a)R. E. Dessy, W. Kitching, and T. Chivers, J . Amer. Chem.Soc., 1966,88,453;

( b ) R. E. Dessy, T .Chivers,and W. Kitching, ibid., p. 467; (c)R.E. Dessy, P. M. Weissman,
and R. L. Pohl, ibid., p. 5117; ( d )R.E. Dessyand P. M. Weissman, ibid., pp. 5124, 5129.
a (a)H. A. Norris, N. I. Kulevsky, 31. Tamres, and S. Searles, Inorg. Chem., 1966,
5, 124; ( b ) A. Mohammed and D. P. N. Satchell, Chem. and I d . , 1966, 2013; (c) D. E.
Young, G. E. McAchan, and S. G. Shore, J . Amer. Chem. doc., 1966, 88, 4390; (d) V.
Gutmaun and E. Wychera, Inorg. Nzcclear Chem. Letters, 1966, 2, 257.
( a )W . Tochtermann, Angew. Chem., Internat. Edn., 1966, 5, 351; (b) W. Sunder-
meyer and W. Verbeek, ibid., p. 1; ( c ) R. D. Chambers and T. Chivers, Organometallic
Chem. Rev., 196G, 1, 279; ( d ) J. S. Thayer, ibid., p. 157; ( e ) 0. M. Nefedov and M . N.
Manakov, Angew. Chem., Internat. Edn., 1966, 5, 1021; (f)E. L. Muetterties and R. A.
Schunn,Quart. Rev., 1966, 20, 245; (9) M. L. Maddox, S . L. Stafford, and H . D. Kaesz,
Adu. Organometallic Chem., 1965, 3, 1.
4 ( a ) I<. M. Mackay, “ Hydrogen Compounds 4 : the Metallic Elements,” E. an:
F. N. Spon, London, 1966; (b) T. C. Waddington, Non-aqueous Solvent Systems,
Academic Press, 1965; ( c ) J. Jander, Chemistry in Liquid Ammonia-I. Inorganic
and General Chemistry in Liquid Ammonia,” Vieweg, Brunswick, and Interscience,
New York-London, 1966.
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D O W N S , EBSWORTH A N D T U R N E R : THE T Y P I C A L E L E M E N T S 139
tials of volatile inorganic compounds has been made,5a and t o the Sadtler
collection of the infrared spectra of 600 inorganic compounds5bhave been
added the spectra of 400 organometallic derivatives.5c
Group 0.-Noble-gas chemistry has been reviewed,6 and noble-gas rad-

iation chemistry discussed.‘ Krypton difjluoride can be prepared by the
exposure of a krypton-fluorine mixture fa daylight;guE(Kr-F) has the
surprisingly low value 8b of 12 kcal.mole-1. There is no evidencegfor the
formation of krypton-oxygen compounds from the ra.dioactive decay of
K83Br0,. The existence of XeF, and XeF, has not been confirmed.1°
Electric discharge in a gas mixture of Xe, F,, and CCl, (or SiC1,) gives
colourless crystals whose vapour shows a mass spectrum containing XeC1-;
the formation of XeC1, is deduced;lla liquid chlorine and gaseous Xe under
pressure slowly formed crysta1s,llb perhaps of XeCI,. Further investi-
gation of the Xe-PtF5 system l 2has led t o the preparation of XeF,+PtF,-,
the XeF5+ion being approximately square-pyramidal [Xe-F(4) = 1.90 8 ;
Xe-F(1) = 1-77 8;F(4)-Xe-F(1) = 83’1. Heat-capacity data suggest
that there are three structural modifications l3 of solid XeF,; the non-
octahedral structure o f gaseous XeF, has been ~ ~ I l f i r r n eand
d , ~the
~ structure
discussed theoretically.15 The magnetic susceptibility16 l7 of solid XeF,
9
indicates the absence of a lom-lying triplet state; the l9F n.m.r. spec-
trum l7 of solid XeF, and the I‘O n.m.r. spectrum l8 of liquid XeOF,
have been examined. Further reported complexes are 4XeF,,SnF4,1g
2XeF,,VF,, 2XeOF,,VF5,20 XeOF,,CsF, 2XeOF4,3RbF, Xe0F4,3KF,
XeOF4,2SbF,,21 XeFG,2NOF,and XeOF,,NOF ; infrared spectra suggest
( a ) H. J. Svec, “Mass Spectrometry,” NATO Adv. Study Inst. Glasgow, 1964
(publ. 1965); (b) “ High Resolution Spectra of Inorganics and Related Compounds,”
Sadtler Research Laboratories, Philadelphia, 1965; ( c ) “ Infrared Grating Spectra of
Organometallic Compounds,” Sadtler Research Laboratories, Philadelphia, 1966.
R. Hoppe, Fortschr. Chem. Forsch., 1965, 5, 213; A. B. Neiding, Russ. Chem.
Rev.,1965, 34, 403; G. J. Moody and J. D. It. Thomas, Rev. Pure AppZ. Chem., 1966,
16, 1.
J. P. Adloff, Radiochim. Acta, 1966, 6, 1 ; G. J. Moody and J. D. R. Thomas,
Nature, 1965, 206, 613.
* (a) L. V. Streng and A. G. Streng, Inorg. Clzem., 1966, 5, 328; (b) S. R. Gunn,
J. Amer. Chem.Xoc., 1966, 88, 5924.
A. N. Murin, T7. D. Nefedov, I. S. Kirin, S. A. Grachev, Yu. K. Gusev, and G. N.
Shaplzin,J. Gen. Chem. (U.S.S.R.), 1965, 35, 2126.
l o R. Weinstock, E. E. Weaver, and C. P. Knop, Inorg. Chem., 1966, 5, 2189.
l1 ( a ) H. Meinert, 2. Chem., 1966, 6, 71; (b) S. F. a.Kettle, Chem. and I n d , , 1966,
1846.
l2 N. Bartlett, F. Einstein, D. F. Stewart, and J. Trotter, Chem. Comm., 1966, 550.
l3 J. G . M a h , F. SchrcL?er, 2nd D. W. Osborne, I n o r g . Nuclear Chem. Letters, 1965,
1, 97.
l4 K. Hedberg, S. H. Peterson, R. R. Ryan, and B. VVeinstock, J . Clzenz. Phys.,
1966, 44, 1726.
l5 R. D. Willett, Theor. Chim. Acta, 1966, 6, 186; L. S. Bartell, Trans. Amer. Cryst.
ASSOC., 1966, 2, 134.
l6 ( a )B. Volaviiek, Monatsh., 1966, 9’7, 1531; (b) H. Selig and F. Schreiner, J . Chem.
Phys., 1966, 45, 4755.
l7 R. Blinc, E. Pirkmajer, J. Slivnik, and I. ZupenEi6, J . Chem. Phys., 1966, 45,
1488.
lS J. Shamir, H. Selig, D. Samuel, and J. Reuben, J . Amer. Chem. Soc., 1965, 87,
2359.
l9 K. E. Pullen and G . H. Cady, Irzorg. Chem., 1966, 5, 2057.
2o G . J. Moody and H. Selig, J . Inorg. Nuclear Chem., 1966, 28, 2429.
a1 H. Selig, Inorg. C h m . , 1966, 5, 183.
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that the last two contain the NO+ion.22 Infrared and X-ray evidence 11~23
indicates that the Xe0,F- ion is not present in CsXe0,F. Mixtures of XeF,
and XeF, in SbF, form green solutions 24 which from their e.s.r. spectra may
contain Xe(m). Raman spectra afford no evidence 25 for the formation of

Xe0,F2 on addition of water to XeOF, in liquid El?; infrared evidence for
the formation of XeOF, at low temperatures has been presented.26 The
preparations of CsHXeO, 27 and Am4(Xe0,),,40H,O 28 have been described.
The negative interaction force constant 29 in KrF, has been simply ex-
~lained.~*
Group 1.-More information about alkali metal solutions in liquid
ammonia and amines emerges from measurements of heats of solution 31a and
electron spin resonance and electronic absorption ~ p e c t r a . 3 ~One
~ conclu-
sion 31b is that the blue diamagnetic species present in moderately concen-
trated solutions is most satisfactorily represented by (e22-)so1v. ; in primary
amines31cRNH2solvated atoms are present as well as solvated electrons, and
the spectroscopic properties are very dependent on R. The inversional
motion of the ammonia molecule may be the basis of the conduction mechan-
ism in dilute solutions of lithium in liquid ammonia.31d Certain properties
of dilute alkali metal-ammonia solutions can be explained 32 by a model
involving equilibria between the solvated metal cation M+ and anion M-,
the solvent S, the anion S-, and the ion-pairs M+M- and M+S-. Proton
n.m.r. spectra of liquid ammonia solutions of alkali salts reflect ion-solvation,
ion-association, and hydrogen-bonding effects.33
Magnetic resonances of the nuclei 23Na,39K, 87Rb, and la3Csin aqueous
alkali salt solutions 34 disclose the following order of increasing shielding by
the anions: I- < Br- < C1- < F- < H20 < NO,-; overlap repulsive forces
between the closed-shellions may account for the observed chemical shifts.
Despite the relative insensitivity t o structural effects, 'Li resonances may
provide information about the solvation of Li+ ions in solution,35and about
organolithium exchange rea~tions.~aBroad-line measurements on poly-
23G. J. Moody and H. Selig, Inorg. Nuclear Chem. Letters, 1966, 2, 319.
23R. D. Peacock, H. Selig, and I. Sheft, J. Inorg. Nuclear Chem., 1966, 28, 2561.
2a B. Cohen and R. D. Peacoolr, J . lnorg. Nuclear Chem., 1966, 28, 3056.
2 6 H. H. Selig, L. A. Quarterman, and H. H. Hyman, J . Inorg. Nuclear Chem.,
1966, 28, 2063.
J. S. Ogden and J. J. Turner, Chem. Comm., 1966, 693.
2 7 B. Jaselkis, T. M. Spittler, and J. L. Huston, J . Amer. Chem. Xoc., 1966, 88,
2149.
Y. Marcus and D. Cohen, Inorg. Chem., 1966, 5, 1740.
2s H. H. Claassen, G. L.Goodman, J. G. Malm, and F. Schreiner, J . Chem. Phys.,
1965, 42, 1229.
ao C. A. Coulson, J . Chem. Phys., 1966, 44, 468.
31 (a)T. R. Tuttle, jun., C. Guttman, and S . Golden, J . Chew. Phys., 1966, 45,
2206; ( b ) R . Catterall and M. C. R. Symons, J. Chem. SOC. ( A ) ,1966, 13; (c) R. Catterall,
M. C. R. Symons, and J. W. Tipping, ibid., p. 1529; ( d ) E. C. Evers and F. R. Longo,
J . Phys. Chem., 1966, 70, 426.
32 S . Golden, C. Guttman, and T. R. Tuttle, jun., J . Chem. Phys., 1966, 44, 3791.
33 A. L. Allred and R. N. Wendriclrs, J. Chem. SOC. ( A ) ,1966, 778.
34 C. Deverell and R. E. Richards, MoZ. Phys., 1966, 10, 551.
s 5 G. E. Maciel, J. K. Hancock, L. F. Lafferty, P. A. Mueller, and W. K. Musker,
Inorg. Chem., 1966, 5, 554.
36 L. M. Seitz and T. L. Brown, J. Amer. Chem. Soc., 1966, 88, 2174, 4140; K. C.
Williams and T. L. Brown, {bid., p. 4134; G. E. Hartwell and T. L.Brown, ibid.,p. 4626.
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D O W N S , E B S W O R T H A N D T U R N E R : THE T Y P I C A L ELEMENTS 141
crystallinelithium compounds 37a reveal structural effects like the two non-
equivalent lithium sites in lithium nitride.37b
Organolithium compoundshave been reviewed.38 Kinetic experiments on
metallation reactions indicate a9a that organolithium aggregates can act as
kinetically active species ; the extent of aggregation in basic solvents

denends on the structure of the organometallic compound.39b Spectro-
scipic data suggest 40 that in but-3-enyl-lithium interadion occurs between
vacant orbitals on the hexameric lithium framework and the n-orbitals of the
butene moiety (1). The formation of specific organolithium-tetrahydrofuran
complexes is revealed by the electronic spectrum of 1,l-diphenyl-n-hexyl-
lithium,41 the acidity of the Li+ cation varying with the extent of solvation.
Evidence from several sources suggest,s that lithium bromide exists as
tetramers in diethyl ether solution.42 Lithium nitroxide, formed through
reaction of lithium atoms and NO in solid argon a t high dilution, has a bent
A
molecule 43 and is probably LiON rather than LiNO (LiON = 100" & 10").
Microwave spectra, 44 of the gaseous hydroxide molecules CsOH and KOH
conform, however, t o the linear-molecule pattern, although a " quasilinear "
structure cannot be excluded.
Group II.-Organoberyllium hydrides, RBeH (R = Me, Et or Ph), can
be prepared as diethyl ether complexes from the appropriate diorgano-
beryllium, beryllium bromide and lithium hydride ;45 the liquid 1 : 1 complex
of methylberyllium hydride is a dimer, [MeBeH,Et,O],. Organoberyllium
hydrides and related compounds add to unsaturated systems like olefins,
aldehydes, and ketones; 45 reaction rates are sensitive to the presence
(a)R. A. Bernheim, I. L. Adler, B. J. Lavmy, D. C. Lini, B. A. Scott, and J. A.
Dixon, J . Chem. Phys., 1966, 45, 3442; ( b ) S . 0. Bishop, P. J. Ring, and P. J. Bray,
ibid., p. 1625.
38 T.L. Brown, Adv. Organometallic Chem., 1965, 3, 365.
39 ( a ) T.L. Brown, J . Organometallic Chem., 1966, 5, 191; R. Waack, P. West, and
M. A. Doran, Chem. and Ind., 1966, 1035; ( b ) R. Waack and P. West, J . Organometallic
Chem., 1966, 5, 188.
4 0 J. P. Oliver, J. B. Smart, and M. T. Emerson, J . Amer. Chem. Xoc., 1966, 88,
2109.
41 R. Waack, M. A. Doran, and P. E. Stevenson, J . Amer. Chem. Soc., 1966, 88,
4101.
4 2 M. Chabanel, J . Chim. phys., 1966, 63, 1143.
4 3 W. L. S. Andrews and G. C. Pimentel, J . Chem. Phys., 1966, 44, 2361.
4 4 R. L. Kuczkowski, D. R. Lide, jun., and L. C. Krisher, J . Chem. Phys., 1966,
44, 3131.
4 6 N. A. Bell and G. E. Coatea, J . C h m . SOC.
( A ) ,1966, 1069.
View Article Online
of ether and to the site of unsaturation in the organic molecule. On

the basis of n.m.r. spectr0scopy,4~ cis-trans isomerism of the dimer
Me,N(Me)BeH,Be(Me)NMe, is indicated. Tetramethyltetrazene reacts with
dialkylberylliums to give both 1 : 1 and 1 : 2 complexes

(Me,N*N=N-NMe2,R2Be)
;47
pyrolysis of the latter leads to polymers of low molecular weight. The
beryllium derivatives of NNN'- trimet hylet hylenediamine, 2-methoxyethanol,
2-&methylaminoethanol, and 2-dimethylaminoethanethiol range from
monomers to polymers.48 Spectroscopic properties of methylberyllium
compounds such as Na2[Me,Be,H,] and trimethylamine and tetramethyl-
ethylenediamine complexes of Me,Be are correlated with the structural units
present,49 and a conformationally labile 6-membered ring structure is
assigned to [MeBeNMe,],. Beryllium borohydride complexes, L,Be(BH,),
(L = Et,O, Me,P, Me2PH, Et,P, Me,", and Me2NH) are liquid a t room
temperature, and monomeric in benzene.50 Interaction of beryllium acetyl-
acetonats with phosphonitrilic derivatives like Ph2P(O)NPPh,OH produces
both mono- and di-substituted monomeric beryllium phosphonitrilates
[typically (2)].51
Ph, ,Ph Ph, ,'Ph CH2 - Me2NL

1
,Me
1
CH2 - MeN
2% NMe -
Ph
I \
Ph
/ \
Ph -Ph
N
'Me
L
NMgS
/
-
i"'
NMe2 CH2
(3)
A review of organomagnesium compounds 52a emphasises that the consti-

tution of Grignard reagents depends on the concentration of the solution and
the nature of the organic group, halogen, and solvent. Current views on
Grignard reagents are radically affected by the ambiguity 52b of the critical
" no-exchange '' experiment involving Mg*Br2 and Et,Mg. In dilute ether
solution, R2Mg and MgX, (R = Et or Ph; X = Br or I) react rapidly
and exothermically, giving solutions indistinguishable from those of the
corresponding Grignard reagents;52c the main reaction appears to be :
R2Mg + MgX2 + ZRMgX,
the equilibrium strongly favouring RMgX. A similar equilibrium with K m 4
is consistent with the polarographic behaviour 5Zd of organomagnesium
species in 1,2-&methoxyethane. In ethereal solutions of the pentafluoro-
phenyl Grignard reagent, C,F,MgBr and (C,F,),Mg (or species based on these
groupings) coexist and exchange rapidly (on an n.m.r. timescale) a t ca.
4c N. A. Bell, G. E. Coates, and J. W. Emsley, J . Chem. SOC.( A ) , 1966, 1360.
47 N. R. Fetter, J . Chem. SOC.( A ) ,1966, 711.
N. A. Bell, J. Chem. SOC. ( A ) , 1966, 548.
4D N. A. Bell, G. E. Coates, and J. W. Emsloy, J . Chem. Soc. ( A ) , 1966, 49.
L. Banford and G. E. Coates, J . Chem. Soc. ( A ) ,1966, 274.
61 K. L. Paciorelr and R. H. Krtttzor, Inorg. Chem., 1966, 5, 638.
6 2 ( a ) B. J. Wakefield, Organometallic C h m . Rev.,1966, 1, 131; (b) R. E. Dessy,
S. E. I. Green, and R. M. Salinger, Tetrahedron Letters, 1964, 1369; ( c ) M. B. Smith
and W. E. Becker, Tetrahedron, 1966,22,3027; ( d )T . Psarras and R. E. Dessy, J . Amer.
Chem. SOC.,1966,88, 5132; (e) D. F. Evans and 35. S. Khan, Chem. Comm., 1966, 67.
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DOWNS, EBSWORTH AND TURNER: THE TYPICAL ELEMENTS 143
90"c. Complexes (1 : 1) of Me,&lg and Ph,Mg with tetramethylethylene-
diamine and 1,Z-dimethoxyethane,monomeric in benzene, have been char-
a ~ t e r i s e dwhereas
,~~ with trimethylethylenediamine Me,Mg gives a dimeric
product, probably with the structure (3). Of the several alkylmagnesium

alkoxides recent,lyprepared,54 only those with chain-branchingat the carbon
atom a to oxygen are tetrameric in benzene; compounds like EtMgOPP and
PriMgOMe under similar conditions have degrees of association of 7-804,
and secondary aminomagnesium alkyls are dimeric, e.g., priMgNPri,],.
Typical of some of the crystalline magnesium alkoxide-ether complexes pre-
pared 54 is a derivative, which, being dimeric in benzene, probably has the
structure (4).
For the gaseous metal dihalide molecules MX, (M = Be, Mg, Ca, Sr, Ba;
X = F, CI, Br, I) the observed geometries are correlated 5 5 with the increas-
ing importance of d-orbitals with increase of atomic number. The octa-
hedral MgCl64- and pyramidal MgC1,- ions have been identified by Raman
spectroscopy 56 in molten MgCl, and MgCl,-KCl, respectively. The so-
called '' alkaline-earth metal carbonyls '' formulated as M(CO), are mixtures
of acetylenediolates, methoxides, and ammonium ~arbonate.~'On the basis
of conductivity and freezing-point measurements, it is suggested 58 that
dissolution of calcium and strontium in their respective molten halides leads
+
to an equilibrium 2M2+ 2e + (M2)2+; (BaJ2+is, however, comparatively
unstable.
Group IIL-Boron. llB n.m.r. spectroscopy remains a fruitful source of
stereochemicalinformation ; recent results include a unique assignment of the
llB spectra of 1,2-dicarbaclovododecaborane59 and 2,4-dicarbaclovohepta-
borane,60confirmation 61 of the previously suggested structures for B&f8,C0
and B,H,,PF3, spectroscopic characterisation of various mono- and di-
alkyldiboranes,62and structural assignments of several new polyborane and
carborane systems subsequently to be described. Extension of the quanti-
tative theory of llB chemical shifts 63 beyond empirical correlations is
53 G . E. Coates and J. A. Heslop, J . Chem. SOC.( A ) ,1966, 26.
64 G . E. Coates and D. Ridley, Chem. Comm., 1066, 560.
5 5 E. F. Hayes, J . Phys. Chenz., 1966, 70, 3740.
5 6 K. Balasubrahmanyan, J . Chem. Phys., 1966, 44, 3270.
5 7 W. Biichner, Helv. Chim. Ada, 1966, 49, 907.
5 8 A. S. Dworkin, H. R. Bronstein, and M. A. Bredig, J . Phys. Chem., 1966, 70,
2384.
69 J. A. Potenza, W. N. Lipscomb, G. D. Vickers, and H. Schroeder, J . Amer.
Chem. SOC.,1966, 88, 628.
6o T. Onak, G. B. Dunks, R. A. Beaudet, and R. L. Poynter, J . Amer. Chena. SOC.,
1966, 88, 4622.
61 A. D. Norman and R. Schaeffer, J . Amer. Chem. Soc., 1966, 88, 1143.
6 2 H. H. Lindner and T. Onak, J . Amer. Chem. SOC., 1966, 88, 1890.
6s F. P. Boer, R. A. Hegstrom, M. D. Newton, J. A. Potenze, and W. N. Lipscomb,
J . Amer. Chern. Xoc., 1966, 88, 6340.
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possible for the icosahedral carboranesfor which the shifts are primarily deter-
mined by differences in paramagnetic shielding. Systematic surveys of
llB n.m.r. spectra show that, in trigonal boron systems, (i) the chemical shift
is determined principally by the atoms directly bound to boron, and (ii)n-

bonding probably contributes to the shielding of the boron.
lH n.m.r. measurements imply that the order of acceptor activity with
respect t o acetonitrile 65a is BBr, > BCl, > BF,, and that the activities of
B(C,F,), and BF, are comparable.65b Comparison of donor and acceptor
strengths has also been an objective of (i) manometric studies of BF, and
BCl, with sulphide ligands 2a and of BF,, BH,, and BMe, with phosphines,66u
(ii) the characterisation of boron halide-phosphorus halide complexes,66b
(iii) displacement reactions, vapour density, and kinetic studies of complexes
of several boron acids? (iv) dissociation pressure measurements of adducts
of Me,N and Me,P with 1,3,2-dioxaborolanand 1,3,2-dioxaborinan(implying
that the &membered ring is the stronger acid).6Gc Differences in acceptor
ability presumably contribute to the variations in charge-transfer spectra and
oxidation potentials of metal cyanide adducts Fe(phen),(CN,BX,), (X = Me,
H, F, C1, and Br) wherein the BX, unit apparently decreases metal-ligand
a-bonding and increases n-bonding. Thermochemical estimates of the B-0
bond energy of the complexes Y,B,OPX, (X, Y = C1 or Br)67 are an order
of magnitude less than " normal " B-0 bond energies. New borane adducts
include a compound with the probable structure H,B,P,O,,BH,, and
L,BH, and L,ZBH, species,68bwhere L is tetramethylethylenediamine, NN'-
dimethylpiperazine, or triethylenediamine. Anomalous variations in the
dipole moments of the amine boranes Me,NH,-,,BH, are attributed 6g t o the
combined polarising influences of the four ligands on the nitrogen lone-pair.
Recent preparative developments have enlarged the range of metal-
boron compounds. Essentially localised metal-boron bonds presumably
exist in the addition compounds L,Rh(CO)X,BY, (L = Ph,P or Ph,As;
X = C1 or Br ; Y = C1 or Br),7Oa (n-C5H,),MH2,BX, and (n-C5HS),ReH,BX,
(M = Mo or W; X = F or Cl),70b and [Cl,M,BX,]- (M == Ge or Sn; X = F
or Cl);?OCthe aflhity of the cyclopentadienyl metal hydrides and MCl,-
ions 7oc for Werent boron acids indicates '' hard base " character for the
metal atoms. Substitution reactions of manganese carbonyls lead to the
formation of Mn-B bonds in compounds of the type X,B*Mn(C0)4Land
XB[Mn(CO),PPh,J, (X = Ph, Bu, C1, NR,,OMe; L = CO or PPh3);'la
6 4 J. E. De Moor and (3. P. Van der Kelen, J . Orgartometallic Chem., 1966, 6, 235;
H. Noth and H. Vahrenkamp, Chem. Ber., 1966, 99, 1049.
6 5 (a)J. M. Miller and M. Onyszchuk, C a d . J . Chem., 1966, 44, 899; (b) A. 0.
Massey and A. J. Park,J . Organmetallic Chem., 1966, 5, 218.
6 6 (a)H. L. Morris, M. Tamres, and S. Searles, Inorg. Chem., 1966, 5,2156; ( b ) A. F.
Armington, J. R. Weiner, and G. H. Moates, &bid.,p. 483; (c) G. E. McAchran and 8.G.
Shore, ibid., p. 2044; ( d ) D. F. Shriver and J. Power, J. Amer. Chem. SOC.,1966, 88,
1672.
6 7 A. Finch, P. J. Gardner, and K. K. Sen Gupta, J . Chem. SOC.( A ) , 1966, 1367.
6 8 ( a ) G. Kodama and H. Kondo, J . Amer. Chewa. Soc., 1966, 88, 2045; ( b ) A. R.
Gatti and T. Wartik, Irtorg. Chem., 1966, 5, 329, 2075.
6 B J. R. Weaver and R. W. Parry, Inorg. Chem., 1966, 5, 713, 718.
7 O ( a )P. Powell and H. Nath, Chem. Comm., 1966,637; ( b ) M. P. Johnson and D. F.
Shiver, J . Amer. Chem. SOC.,1966,88, 301; ( c ) M. P. Johnson, D. F. Shiver, and S. A.
Shiver, &bid.,p. 1588.
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D O W N S , EBSWORl'H A N D T U R N E R : T H E T Y P I C A L ELEMENTS 145
1lB magnetic resonances of new compounds suggest substantial back-
donation of metald-electronsto the boron. Analogous compounds of cobalt and
platinum, viz., (Ph,PCH,CH,PPh,), Co(BPh,), and (Et,P),Pt(BPh,)Cl, have
been ~repared.71~ Metal atoms have also been incorporated into delocalised
bonding units. Thus, metallation of decaborane is believed to give solvated
complexes wherein the metal atom (Al, Zn, or Cd) bridges the 6,9 positions of
decaborane.72 Two carborane derivatives in which a metal atom occupies
the twelfth icosahedral position in the otherwise open face of the C,B,Hll2-
(or related) anion have been structurally characterised by X-ray methods ;
the proposed structure of the [C,BsH,,Re(CO),]- ion has thus been con-
hrmed,73Qwhilst a new palladium compound 730 containing a tetraphenyl-
cyclobutadiene ring and the [B&,C2Me212- ion has a similar structure (5).
Ph
Ph
(5)
[Reproduced from P. A. Wegner and M. F. Hawthorne, Chem. Comm., 1966, 861.1
General reviews about B,-B, boron h y d r i d e ~ ,carboranes,

~*~ 7Pb* and
organo-substituted boranes 74b have appeared. The theoretical aspects of
bonding in boron hydrides continue to attract attention : Slater-type atomic
' (u) H. Noth and G. Schmid, 2. anorg. Chem., 1966, 345, 69; J. Organometallic
l
O h m . , 1966, 5, 109; ( b ) G. Schmid and H. Noth, 2. Naturforsch., 1965, 20b, 1008.
7 8 N. N. Greenwood and J. A. McGinnety, J . Chem. SOC. ( A ) , 1966, 1090; N. N.
Greenwood and N. F. Travers, Imrg. Nuclear Chern. Letters, 1966, 2, 169.
7s (a)A. Zalkin, T. E. Hopkins, and D. H. Templeton, Inorg. Chem., 1966, 5, 1189;
Ann. Reports, 1965, 62, 139; ( b ) P. A. Wegner and M. F. Hawthorne, Chem. Cmm.,
1966, 861.
7 4 (a)B. M. Mikhailov and M. E. Kuimova, Rms. Chem. Rev., 1966,35, 569; ( b ) T.
Onak, Adv. OrgunometallicChem., 1965,3,263 ;( c ) K. Issleib, R. Lindner, and A. Tzschach,
2.Chem., 1966, 8, 1.
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basis functions have been used vSu to examine molecular charge distributions,
overlap populations, and other properties of some boron hydrides; for the
general three-centre two-electron system ZHZ, the energy, ZHZ bond angle,
and effective nuclear charge of Z are closely interrelated;75bapplication of

LC(Hartree-Fock)AO molecular orbital theory to the c2H6 and BaHs mole- .
cules indicates 75c that the different geometries hinge upon the contributions
of the heavy atom p-functions to molecular bonding. Mass-spectrometric
procedures have been devised to identify labile borane s p e c i e ~ . ~Hence,
6~ the
pyrolysis of tetraborane(10) has been shown 76b to produce B,H, as well as di-,
penta-, hexa-, hepta-, octa-, and deca-boranes, and possibly nonaborane.
Monomeric BH, has been clearly identified 76c in the pyrolysis of diborane, as
have the new molecular species H,&@, and H4B607(probably boroxine deri-
vatives) in the high-temperature reaction of boron with water vapour.76d
Similarly, the anions BH4-, B2H,-, B2H8-, B3H8-, B3H7-, B,H,-, B,H,-,
and B5H1,- (all with lifetimes > 10-5 see.) have been identified 7Oe when
B2H6 is bombarded by krypton ions.
The BH, groups of zirconium and hafnium borohydrides 7 7 a are bonded
to the metal by hydrogen bridges, though a rapid exchange process renders
the bridge and terminal hydrogens magnetically equivalent ; the boro-

hydrides of zirconium and hafnium (but not of titanium and copper)
react with donor molecules 77b to give metal hydride derivatives [e.g.,
(n-C5H,),Zr(H)BH4]. The reaction of bis(triphenylphosphine)copper(I)
borohydride with strong acids 78 gives salts containing the binuclear cation
[L2CuBH4CuL2]+(L = PPh,), the i.r. spectrum and reactions of which
suggest the structure (6). C1MgBH4,2THF (TI33 = tetrahydrofuran) is
dimeric in benzene solution with a dipole moment of 6 ~ but , monomeric
in tetrahydrof~ran.7~Octahydrotriborates, e.g., Mg(B,H&,(THF), and
Mg(BH4)(B,H,),5THF, have been prepared by heating B2H6 with the
7 6 (a) I?. P. Boer, M. D. Newton, and W. N. Lipscomb, J. Amer. C h m . SOC., 1966,
88, 2361; W. E. Palke and W. N. Lipscomb, ibid., p. 2384; (b) K. E. Banyard and N.
Shull, J. Chem. Phys., 1966, 44, 384; (c) R. J. Buenker, S. D. Peyerimhoff, L. C. Allen,
and J. L. Whitten, ibid., 1966, 45, 2835.
713 (a) A. D. Norman, It. Schaeffer, A. B. Baylis, G . A. Pressley, jun., and F. E.
Stafford, J. Amer. Chem. SOC.,1966, 88, 2151; (b)A. B. Baylis, G. A. Pressley, jun.,
M. E. Gordon, and F. E. Stafford, ibid., p. 929; (c) A. B. Baylis, G. A. Pressley, jun.,
and F. E. Stafford, ibid., p. 2428; (d)S. K. Gupta and R. F. Porter, J. Phys. Chem.,
1966, 70, 871; (e) Gr. Hortig, 0.Midler, K. R. Schubert, and E. Fluck, 2.Naturforsch.,
1966, 21b, 609.
7 7 ( u ) B. D. James, R. K. Nanda, and M. G. H. Wallbridge, J. Chem. SOC.( A ) ,
1966, 182; (b) B. D. James, R. K. Nanda, and M. G. H. Wallbridge, C h m . Comm.,
1966, 849.
7 8 I?. Cariati and L.Naldini, J. Inorg. Nuclear Chem., 1966, 28, 2243.
7 9 W. E. Becker and E. C. Ashby, Inorg. Chena., 1965, 4, 1816.
8 0 S. He3mAnek and J. Plegek, CoZZ. Czech. Cham. Comm., 1966,31, 177.
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DOWNS, EBSWORTH AND T U R N E R : THE TYPICAL ELEMENTS 147
appropriate tetrahydroborate in ether solution. Sodium borohydride reacts
with aziridine in moist tetrahydrofuran,gl giving, probably, 1,2-azaboretidine
(7). Spectroscopic evidence 82 suggests the formation of the HSBH,- anion
and probably (HS),BH,- in the thiohydrolysis of LiBH, in tetrahydrofuran

solutions a t -22-0"; warming the solution to 30" probably produces poly-
mers of the species SBH,-. In the substituted monoborane HB(OCD,), the
B-H bond length is curiously long (1.24 A ) , S 3 being almost identical with
that for BH,-. Properties of lithiomethyldimethylamine(dimethylamino-
methyl)dihydroborane,84isolated from the reaction of butyl-lithium with
[H2B(NMe,),]C1, favour the cyclic structure (8a.); hydrolysis or reaction with
methyl iodide convert the compound into the new borane cations (8b) or (8c),
respectively. I n the novel amine Me,N*BH,*CH,-NMe, the BH2 group
enhances the basicity of the amine,84 the borane adduct of which,
Me,N*BH,*CH,*NMe,,BH,, sublimes unchanged in vacuo at 100".
Independent investigations 7 G C 9 85 suggest that the enthalpy for the pro-
cess B,H,(g) + 2BH,(g) is 35 kcal./mole. Hydrogen-evolution measure-
ments during the hydrolysis of B,H, and BH,- are concordant s with the
formation of the intermediates BH,+aq., BH(OH),, or BH(OH),- according
H,B-CH,.NMe, H,B*CH,.NHMe,+ H,B*CH,*NMe,+
! - 1 I 1
to whether the medium is acid, neutral, or alkaline, respectively. 1lB n.m.r.

spectra support 8Ya the formation of singly hydrogen-bridged amine-boranes
H,B-H-BH,-NH,Me,-, (n = 0, 2, or 3) €Tom B,H, and the appropriate
amine a t -78"; with 1 mol. of amine the amine-boranes give the unsym-
metrical cleavage products [BH2(NH,Me,-,J2][BH4]. The structure
[Me2B(NH3)2]+[H,Bhle,]-is proposed 87b for the product of the direct reac-
tion of ammonia and tetramethyldiborane, whereas in ethereal solution the
non-electrolyte Me,BH,NR, is formed. For the dimethylammoniate of
diborane the formulation [H,B(NH,Me),] +[BHa]- is favoured.ss With allene
B2H6 undergoes terminal addition g9 producing 1,%trimethylenediborane (9),
noteworthy for its reversible polperisation.
Reaction of acetylene and B2H6 in an electric discharge 90a yields, as the
major volatile products, the carboranes 1,6-C,B,H5, 1,6-C,B4H6, 2,4-C2B,H,,
81 S . Akerfeldt and M. Hellstrom, Acta. Chem. Scand., 1966, 20, 1418.

82 B. F. Spielvogel and E. F. Rothgery, Chem. Comm., 1966, 765.
T. C. Farrar, J. Cooper, and T. D. Coyle, Chem. Conam., 1966, 610.
N. E. Miller, J . Amer. Chem. Xoc., 1966, 88, 4284.
8 5 J. Grotewold, E. A. Lissi, and A. E. Villa, J. Chem. SOC. ( A ) , 1966, 1038; A. B.
Burg and Y.-C. Fu, J. Amer. Chem. SOC.,1966, 88, 1147.
8 6 W. L. Jolly and T. Schmitt, J. Amer. Chem. Xoc., 1966, 88, 4282.
( a ) S. G. Shore and C. L. Hall, J . Amer. Chem. SOC.,1966, 88, 5346; ( b ) P. C.
Moews, jun., and R. W. Parry, Inorg. Chem., 1966, 5, 1552.
0. T. Beachley, Inorg. Chein., 1965, 4, 1823.
H. H. Lindner and T. Onak, J . Amer. Clwm. SOC.,1966, 88, 1886.
(a)R. N. Grimes, J. Amer. Chem. Xoc., 1966, 88, 1895; ( b ) R. N. Grimes, ibid.,
p. 1070; ( c ) R. Koster, H.-J. Horstschiifer, and P. Binger, Angew. Chwn., Internat. Edn.,
1966, 5, 730.
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148 INORGANIC CHEMISTBY
B-methylated derivatives of these, and C,3-Me,-1,2-C2B,H3 [see (lo)], the last

of which represents a new isomer of the C2B3H5system with one equatorial
and one apical carbon atom in the trigonal-bipyramidal framework.90b
Hydroboration of alkynylboranes by alkyldiboranes also affords substituted

C2B3 carb0ranes.m The base-catalysed rearrangement of 1,2- to 2,3-
dimethylpentaborane(9) (11) has been estab1i~hed;~lthere are signs of
weakening of the B-B bond of the basal Me-B-B-Me unit relative to
H-B-B-H. The AlC1,-catalysed chlorination of pentaborane(9) probably
involves electrophilic attack of the borane cage by C1+ (giving l-chloro-
pentaborane), whereas the uncatalysed reaction proceeds through radical
formation (givingmainly 2-~hloropentaborane).~2 Mono-, Q3a9 di-,Q”tri-,9”
and tetracarbahexaboranes sge have now been characterised. The respective
parent compounds 2-CB,Hg, 2,3-C,B,H8, 2,3,4-C3B,H,, and 2,3,4,5-C4B,H,
are structurally related to the B,H,, molecule by successive substitution of
CH for isoelectronic BH, groups in the basal plane (12). With NaH in
diglyme, 2,3-C2B4Hssuffers reversible loss of one of the bridge hydrogens to
form the 2,3-C,B4H,- Alkylated 2,4-dicarbaclovoheptaboranes(7)
are produced together with monocarbahexaboranes(9)by the dehalogenation
of organofluoroboranes.93b Mass-spectrometric techniques g4 permit the
identification of the boranes BsH12 and B9Hl, originating from the reaction
between liquid B,Hll and gaseous ; earlier reports of heptaboranes are
questioned. With the synthesis of B7C,Hg and two isomeric BsC2H1,
, ~ ~series B,C,H,+,
systems, and an improved route to BsCzHs c a r b ~ r a n e sthe
has been completed from n = 3 t o 10; tentative structural assignments are
given (13). The thermal isomerisation of B,HsC,Me2 at m. 350” is clearly
reminiscent of the behaviour of icosahedral carboranesmg5Oxidation of the
corresponding B,C2H11carborane gives dicarbanonaboranes(13),B7C2H1,RR’
(R,R= H, Me, or Ph) 96 for which the structure (14)is proposed. With
aqueous alkali B7C,Hl,Me, forms B7C,H,,Me2-, whilst pyrolysis of the dicar-
banonaboranes produces BnC2Hn+2 carboranes. Salts of two novel poly-
hedral borane anions BQHg2-and BllHl12-, from the thermal decomposition
of the corresponding salts of the B3H,- and B11H132-ions, respectively, me
thermally, though not hydrolytically, In solution the BQHQ2- ion
appears to have a tricapped trigonal-prismatic structure [see (13)].
Decaborane(14) does not fit well into a thermochemicctl bond-energy
scheme with the lower b~ranes.~g Noteworthy developments in decaborane
91 T. Onak, L. B. Friedman, J. A. Hartsuck, and W. N. Lipscomb, J . Amer. Chm.

SOC., 1966, 88,3439; L. B. Friedman and W. N. Lipscomb, Inorg. Chern., 1966, 5, 1752.
1966, 88, 4528.
9 2 D. F. Gaines, J . A m r . Chem. SOC.,
s3 ( a )T. P. Onak, 0.B. Dunks, J. R. Spielman, F. J. Gerhart, and R. E. Williams,
J . Amer. Chem. Xoc., 1966,88,2061; ( 6 ) R. Koster and M. A. Grassberger, Amgew. Chem.,
Internat. Edn., 1966, 5, 580; (c) T. Onak and G. B. Dunks, Inorg. Chem., 1966, 6, 439;
( d )C. L. Bramlett and R. N. Grimes, J.Amer. Chern. SOC.,1966,88,4269; (e) P. Binger,
Tetrahedron Letters, 1966, 2675.
0 4 J. F. Ditter, J. R. Spielman, and R. E. Williams, Inorg. Chem., 1966, 5, 118.
9 5 F. N. Tebbe, P. M. Garrett, D. C. Young, and M. F. Hawthorne, J. Amer. C h .
SOC.,1966, 88, 609.
9 6 F. N. Tebbe, P. M. Garrett, and M. F. Hawthorne, J . Arner. Chern. Soc., 1966,
88, 607.
9 7 F. Klanberg and E. L. Muetterties, Inorg. Chem., 1966, 5, 1955.
g 8 S. R . Gunn and J. H. Kindsvater, J . Phys. Chem., 1966,70,1114.
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D O W N S , EBSWORTH A N D T U R N E R : THE TYPICAL ELEMENTS 149
I
Arc hi m e d e a n B7C2H9
anti prism
Tr i capped
trigonal prism B i capped A r c h imedean
(13) antipr ism
0.P o s s i b l e p o s i t i o n s
for C atoms
chemistry include the metallation reactions,72 identification of two isomeric
B10H13NH3- ions distinguishable by their susceptibility to nucleophilic
characterisation 100 of the salt Na2B,,Hlz, and n.m.r. evidence lol
that the adduct BloH1,,2DMF (DMI? = dimethylformamide) contains
the units B-0-CH=NMe,. Diazonium derivatives formulated as
l,lO-+N,Blo~-X,N,+ (X = H, C1, or I) undergo nucleophilic replacement
reactions and are thus useful synthetic intermediates ;lo2 substitution of CN-,
N3-, or OCN- for halogen in polyhalogenated BloHl02-and B12H122-deri-
vatives can also be effected by photolysis.lO3 The oxidation of polyhedral
boranes produces free radica1~,~04 which, according to kinetic measurements,
constitute the &st step in the oxidative coupling of Bl0H,,Z- ions giving Bzo
species; since the radicals produced from B1,HlO2-and B,,H1,0H4- appear
similar, boron cages joined by a B-B bond probably remain electronically
isolated. The new undecaborane BllH15, prepared in solvated form by
acidification of NaBl1H1, in non-aqueous solution,l05 reacts with water,
alcohol, or organic sulphides, producing a second new, solvated undecaborane
B,lHl,. For the unusual 1 : 1 adducts of decaborane(l4) with alkyl isocya-
nides, the zwitterionic structure R+NR2-[CBloHl2-] is suggested, the carbon
atom forming part of the open face of an ll-particle icosahedral fragment.lo6
A similar unit is found in the C,B,H,l-metal derivatives and, according
to spectroscopicevidence, in the dicarbaundecaborate anions R’R’’C,B,H,X-
(R = H, Me, or Ph; X = Br or I) where the substituents R‘, R”,and X are
O g E. L. Muetterties and F. Klanberg, Imrg. Chem., 1966, 5, 315.
1966, 88, 3441.
l o oP. H. Wilks and J. C. Carter, J . Amer. Chem. SOC.,
Iol W. R. Hertler and E. L. Muetterties, Inorg. Chem., 1966, 5, 160.
lo2 W. H. Knoth, J . A m r . Chent. Soc., 1966, 88, 935.
lo3S. Trohenko, J . Amer. Chem. Soc., 1966, 88, 1899.
Io4 J. S. Lewis and A. Kaczmarczyk, J . Amer. C h m . Soc., 1966, 88, 1068; R. L.
Middaugh and F. Farha, jun., ibid., p. 4147.
Io5 L. J. Edwards and J. M. Makhlouf, J . Amer. C h m . SOC., 1966, 88, 4728.
Io6 D. E. Hyatt, D. A. Owen, and L. J. Todd, Irwrg. Chena., 1966, 5, 1749.
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150 I N O R U A N I C CHEMISTRY
attached, respectively, to adjacent C, C, and B atoms of the open face.lO7a In

the neutral dicarbaundecaboranes(13) R’R”C2BgHloX,two protons appear
to be weakly bound to boron atoms in the open face;1°7a species of this type,
viz. ,X2C2BgHIl,are also formed by alcoholic cleavage of CC‘-dihalogeno-

carboranes, l,2-~C,B1,Hl,. Since, in the reaction of piperidine with mono-
and di-C-substituted derivatives of 1,2-C2B10H12, asymmetrically substituted
carboranes give only one correspondingly substituted C,BgH12- anion,l08
boron-elimination probably occurs at the 3,6 positions of the C,Bl0 cage
where the electron density is lowest. The skeleton of the dicarbaunde-
caborane(1l),Me2C2BsHg, consists of a boron-bridged BloH1,-like framework
with carbon atoms in the 6,9 po~itions;~OS the B11H112- ion should be struc-
turally analog0us.~7
(-H7H/-H
B T
HB CI, ,CI
Pd
Ph2P
\ /
H,
R’ ’ H \
R’
(14)
The positions of electrophilic bromination of 1,2-dicarbaclovododeca-
borane(12) and its 1,2-dimethylderivative have been established by crystal-
lographic studies of the products;59,l10 the order of substitution is B-9,12 and
then B-8,10, the four most electron-richsites according to molecular orbital
calculations. This order is supported by the fact that electrophilic halo-
genation of a 1-organo-1,2-carboranegives two monohalogenocarboranesbut
only one dihalogenocarborane,llla and by the synthesis (from appropriate
halogenodecaboranes and acetylenes) of carboranes containing halogen
atoms in specific 1ocations.lllb There is evidence of increased electron
density in the carborane nucleus of 1,2-Me2C2BloHlocompared with
1,2-H2C2B10H10, though contrary t o some reports,l10 tetrabromo-derivatives
of both have in fact been obtained.lllc 1,7-Dicarbaclovododecaboranes(m-
carboranes) can be similarly halogenated, the sites of attack being initially
B-9,10 (on the strength of electron densities and number of isomers ob-
tained).llld The mechanism of the thermal isomerisation of icosahedral car-
boranes (and similar rearrangements) has been discussed. l2a Bulky R,Si
substituents attached to the carbon atoms of the o-carborane cage facilitate
isomerisation, suggesting that steric factors are important,112b and activation
lo7( a ) F. P. Olsen and M. F. Hawthorne, I n o r g . Chem., 1965, 4, 1839; ( 6 ) L. I.
Zakharkin and L. S. Podvisotskaya, Bull. A d . Sci. U.S.S.R., 1966, 742.
108 L. I. Zakharkin and V. N. Kalinin, Doklady Chem., 1965, 163,631.
l o a C.-c. Tsai and W. E. Streib, J . Amer. Chem. Xoc., 1966, 88, 4513.
110 J. A. Potenza and W. N. Lipscomb, Inorg. Cherrz., 1966, 5, 1471, 1478, 1483.
111 ( a ) L. I. Zakharkin and V. N. Kalinin, Bull. Acad. Sci. U.X.X.R., 1965, 1287;
( b ) L. I. Zakharkin and V. N. Kalinin, ibid., 1966, 566; ( c ) Idem, ibid., p. 549; (d) L. I.
Zakharkin and V. N. Kalinin, Doklady Akad. Nauk. S.X.S.R., 1966, 169, 590.
112 (a)W. N.Lipscomb, Science, 1966, 153, 373; (b) R.M. Salinger and C. L. Frye,
Imrg. Chem., 1965, 4, 1815.
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DOWNS, EBSWORTH AND T U R N E R : THE TYPICAL ELEMENTS 151
enthalpies imply that some skeletal deformation required in the transition
state is already present in the ground sta,te of the substituted carboranes.
With the synthesis of C-carboranyl alkanes,113a cycloalkane d e r i ~ a t i v e s , l l ~ ~
carboxylic acids,l1* alcohols, 3d amines, 11%halides,llgf ketones,ll3g and

substituted phenyl derivatives,113han extensive organic chemistry of car-
boranes is taking shape. The range of boron-substituents is more limited,
but, apart from B-halogeno-compounds, B-monohydroxy-derivativeshave
also been synthesised.ll* The electron-attractingpropensity of the carborane
nucleus is evident from the acidity of 1,2-bis(hydroxymethyl)-o-carborane,
and the weak basicity of the 1,2-bis(aminomethyl)-compound,113i the
decarboxylation of carboranylcarboxylicacids by metal acetylacetonates,11*
the ‘‘ positive ” character of the halogen in C-halogeno~arboranes,l~~f and
the influence of the carboranyl group on aromatic substitution reactions of
pheny1~arboranes.l~~~ Numerous facts, e.g., the relative dissociation con-
stants of corresponding carboxylic acids,ll& suggest that the order of
acceptor power is : o-carborane>m-carborane. The coloured paramagnetic
solutions formed from aryl-substituted 1,2-carboranes and potassium in an
ether solvent presumably contain anion free-radicals, the electron spin
resonance spectra of which suggest a highly delocalised unpaircd electron,l15
whereas the diamagnetic solution formed from vinylcarborane is believed t o
contain a dimeric dianion. Bis-1,2-carborane is composed of two C2B,,
icosahedra joined by a C-C singlebond.l16 Couplingreactions of m-carboranes
tendto givepolymerswith,for example, bridging carbonyl,113b d i ~ r g a n o t i n , l l ~ ~
c h l o r ~ p h o s p h i n eor
, ~siloxane
~~~ 117c groups. C-Substituted sulphurll8U and
phosphorus llSbderivatives of o-carboranes form metal chelate systems
[typically(15)]. The remarkable resistance to electrophilic attack of C-
carboranyl mercury compounds is attributed l18C to the combination of
unusual co-ordination of the carboranyl carbon atom, steric hindrance, and
acceptor properties of the carborane nucleus.
113 ( a ) L. I. Zakharkin and A. V . Kazantsev, Bull. Acad. Sci. U.S.S.R., 1965, 2153;
( b ) J. P. Reiner, R. P. Alexander, and H. Schroeder, Inorg. C h m . , 1966, 5, 1460; L. I.
Zakharkin, Bull. Acad. Sci. U.S.S.R..1965, 1083; (c) L. D. Hansen, J. A. Partridge,
R. M. Izatt, and J. J. Christensen, Inorg. Chem., 1966, 5, 569; V. I. Stanko and A. I.
Klimova, J . Gen. Chern. (U.S.S.R.), 1966, 36, 165; N. R. Fetter, Canad. J . Ch m . , 1966,
44, 1463; ( d ) L. I. Zakharkin and A. V . Kazantsev, Bull. Acad. Sci. U.S.S.R., 1966,
1128; ( e ) L. I. Zakharkin and V. N. Kalinin, J. Gem. Chem. (U.S.S.R.), 1965, 35, 1878;
(f)L. I. Zakharkin and L. S. Podvisotskaya, Bull. A d . Sci. U.S.S.R.,1965, 1422;
( 9 ) L..I. Zakharkin and A. I. L’vov, ibid., 1966, 128; (h) L. I. Zakharkin and V. N.
K a h , zbid., 1965, 2173; Dolcludy Chem., 1965, 164, 904; (i) T. V. Potapova, R. A.
Svitsyn, A. F. Zhigach, V. T. Laptev, I. V. Persianova, and P. Z. Sorokin, Buss. J .
Inorg. Chem., 1965, 10, 1133.
114 L.I. Zakharkin, V. N. Kalinin, and L.S. Podvisotskaya, Bull. Acad. Sci. U.S.S.R.,
1965, 1684.
116 K. A. Bilevich, L. I. Zakharkin, and 0. Yu. Okhlobystin, Bull. Acad. Sci.
U.S.S.R., 1965, 1887.
llS L. H. Hall, A. Perloff, F. A. Mauer, and S. Block, J . Chem. Phys., 1965,43, 3911.
11’ ( a )S. Bresadola, F . Rossetto, and G. Tagliavini,Chem. C m m . , 1966, 623; ( b ) R . I?.
Alexander and H. Schroeder, Inorg. Chem., 1966, 5 , 4 9 3 ; ( c ) S. Papetti, B. B. Schaeffer,
A. P. Gray, and T. L. Heying, J . Polymer Sci., Pt. A-1, 1966, 4, 1623.
118 ( a ) H.D. Smith, jun., C. 0. Obenland, and S. Papetti, Inorg. Chem., 1966, 5,
1013; ( b ) L. I. Zakharkin and G. G. Zhigareva, Bull. Acad. Sci. U.S.S.R., 1965, 905;
(c) L. I. Zakharkin, V. I. Bregadze, and 0. Yu. Okhlobystin, J . OrgawrnetaElic Ohm.,
1966, 6, 228.
View Article Online
[Reproduced from M. F. Hawthorne and R.L.Pilling, J . Amer. Chem. Soc.,1966,:88,

3873.1
(17b)
The BZOHIa2- ion undergoes reversiblei s o m e r i s a t i ~ nto
, ~give
~ ~ a “ photo ”
ion probably having the structure indicated (16). Another remarkable
polyborane, the adduct B2,H1,,3MeCN, contains the molecular unit
B20H,a(NCMe)2 with the structure (17a),whose formation involves rearrange-
ment of the B,, unit of B,H1, (17b), giving a new framework composed of
B1,and B,, icosahedral units with a common triangular face.120
The synthesis of organohalogenoboranes has been reviewed,lzl and
differences in disproportionation tendencies of alkylhalogenoboranes,122
apparently due to thermodynamic factors, have been discussed. The difunc-
tional Lewis acid 1,Z-bis(difluorobory1)ethaneforms adducts of the type
C2H4(BF2),,2D(D = Me,O or THF),123but with (Ph&O or MeOCPh,,
1 : 1 complexes also result, probably with the structure (18). Infrared spectra
of BE’, trapped in low-temperature matrices support earlier evidence of
lD M. F.Hawthorne and R. L. Pilling, J . Amer. Chem. Soc., 1966, 88, 3873.
1 2 0 J. H.Enernark, L. B. Friedman, and W. N. Lipscomb, Inorg. Chem., 1966, 5,
2168.
121 K. Niedenzu, Organometallk Chm. Rev., 1966, 1, 305.
122 P.A. McCusker and J. H. Bright, J. Inorg. Nuclear Chem., 1966, 28, 2261
18s M. J. Biallas and D. F. Shiver, J . Amer. Chem. SOC.,1966, 88, 375.
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D O W N S , E B S W O R T H A N D ‘ T U R N E R : THE TYPICAL E L E M E N T S 153
association,12* being compatible with the formation of a bridged h e r
species. Evidence is also presented 125 supporting the formation of the
B,F,- ion in the reaction of amine tetrafluoroborates with BF,. To clarify
the status of certain fluoroborates, the interrelationship of the four primary

compounds BF,, B,O,, HI?, and H20has been expressed in the form of a
“ genealogical tree.” 126 Solvent- and concentration-dependent llB and
19F n.m.r. parameters of the BF4- ion have been related to solvation
effects.127 The redistribution behaviour of boron halides and properties of
the mixed halides have been correlated 128 with n-bonding effects.
n-Bonding in aminoboranes has been the subject of molecular orbital cal-

culations, and mass-spectrometric measurements.129aP b Analysis of the
vibrational spectra of l0B-substituted dialkylaminoboranes, confirming the
interaction of B-N and G N stretching vibrations, 1m shows that infrared
frequency shifts attributed to B-N motions are not reliable indices of z-
bonding; the same cautionary note applies to borazine systems.l3Qb The
factors controlling the polymerisation of aminoboranes have been elabor-
ated. l S 1 Novel aminoboranes include various N-silyl deri~atives.13~a~ b Di-
p-tolylcarbodi-imide reacts with B-X groups (X = C1, Br, Ph, OMe,
NEt,, or SBun) by insertion, to give substituted aminoboranes, e.g.,
Y,B*NTol*C(:NTol)*X,whence the relative migratory aptitudes of different
groups has been deduced.lS3 Dehydrohalogenationof amine-boranes affords
a useful route to a m i n ~ b o r a n e sbut
, ~ ~only
~ ~ bulky amines like Et,N effect
this change 134 in C1,B,NHMe2; other amines yield, under similar conditions,
bis-amine complexes formulated as [Amine(Me,hTH)BCl,]Cl. Properties of
the aminoboranes include the formation of charge-transfer complexes with
iodine, 35a thermal elimination reactions giving cyclic B-N compounds,1S2b
lZ4 J. M. Bassler, P. L. Timms, and J. L. Margrave, J. Chem. Phys., 1966, 45, 2704;
cf. R. G. Steinhardt, jun., G . E. S. Fetsch and M. W. Jordan, ibid., 1965, 43, 4528.
lZ5 J. J. Harris, Inorg. Chem., 1966, 5, 1627.
l Z 6S. Pawlenko, 2. unorg. Chem., 1966, 547, 1, 7.
lZ7 R. Haque and L. W. Reeves, J. Phys. Ciaem., 1966, 70, 2753; R . J. Gillespie
and J. S. Hartman, J. Chem. Phys., 1966, 45, 2712.
M. F. Lappert, J. B. Pedley, P. N. K. Riley, and A. Tweedale, Chern. Comm.,
1966, 788.
12* ( a )P. G. Perlks and D. H. Wall, J. Chem.SOC. ( A ) ,1966, 1207; (b) J. C. Baldwin,
M. F. Lappert, J. B. Pedley, P. N. K. Riley, and R. D. Sedgwick, Inorg. Nuclear Chem.
Letters, 1965, 1, 57.
130 (a) H. J. Becher and H. T. Baechle, 2. ghys. Chem. (Frankfurt), 1966, 48, 359;
(b) R. E. Hester and C. W. J. Scaife, Spectrochim. Acta, 1966, 22, 455, 755.
131 M. F. Lappert, M. K. Majumdar, and B. P. Tilley, J. Chern. SOC. ( A ) , 1966, 1590.
132 (a) R. L. Wells and A. L. Collins, Inorg. Chem., 1966, 5, 1327; (b) P. Ceymayer
and E. G. Rochow, Monatsh., 1966, 97, 429, 437.
133 R. Jefferson, M. F. Lappert, B. Prokai, and B. P . Tilley, J. Chem. SOC.( A ) ,
1966, 1584.
134 H. Noth, P. Schweizer, and F. Ziegelgansberger, Chena. Ber., 1966, 99, 1089.
135 ( a ) I. D. Eubanks and J. J. Lagowski, J. Amer. Chem. SOC.,1966, 88, 2425;
(b) N. N. Greenwood and J. Walker, Inorg. Nuclear Chem. Letters, 1965, 1, 65.
View Article Online
~ ~ 5 ~ studies of which indicate the sequence

and redistribution r e a ~ t i o n s , n.m.r.
<
MezNBX2 Et,NBX, < BX, < PhBX, for the relative rates of halide
exchange. Monomeric boron imides, C,FE',B:NAr (Ar = p-T/leO*C,H, or
mesityl), are produced 136 [with small amounts of the dimer (C,F,B*NAr)g
when Ar = p-MeO*C,H4] from C,F,BCl, and ArNH,. Dimethylboron
azide 13' associates reversibly in the liquid phase and forms 1 : 1 complexes
with bases like pyridine.
Apart from proton n.rn.r. surveys 138 and vibrational analyses,13*bmost
of the advances in borazine chemistry have been associated with preparative
reactions ;139a among the new borazines synthesized are fluoro-aryland -alkyl
derivatives,139bLinear polyborazines (formed by condensation reactions of
simple borazines with diamines),lZgcand hydrolytically stable derivatives
with bulky B - s u b s t i t ~ e n t s . ~ ~ ~ reaction
The ~ of B-trichloroborazine with
MeMgBr is reported to give a polycyclic B-methylborazine, but whether this
has a naphthalene- or biphenyl-like structure has yet to be re~olved.139~
More derivatives of the cyclotetrazenoborane system have been charac-
terised, thus confirming the generality of the preparative reaction between
primary amine-boranes and organic azides.140 Compounds containing boron
bonded to the nitrogen of a pyrazole nucleus l 4 l may take the form of B-N
heterocycles and metal chelates. Cyclic species of composition (BH2NH2),
(n= 2, 3, 5, and possibly 4),resulting from the reaction of NaNH, with
[H2B(NH3),]BH, in liquid ammonia, have also been described,l42 as have
members of a new class of heterocyclescontainingthe elementsboron, nitrogen,
and phosphorus in the same ring.143 The preparation of numerous hetero-
cycles containing carbon as well as boron and nitrogen has been r e p ~ r t e d , l ~ * ~
for example, by the reaction of am-diamines with amin0boranes.l4*~ The
dimethylaminomethylborane cyclic dirner, [H,B*CH,*NMe,],, is relatively
stable with respect to thermal dissociation, unlike the analogous amino-
methyl(dimethy1)borane;145 this is in line with simple Lewis acid-base
affinities.
Some characteristic features of the crystal chemistry of borates hare been
outlined,146 and a review of organosulphur-boron compounds l 4 7 has
136 P. I. Paet,zold and W. M. Sirnson, Angew. Chem., Internat. Edn., 1966, 5, 842.
P. I. Paetzold and H. J. Hansen, 2. anorg. Chem., 1966, 345, 79.
13* A. Grace and P. Powell, J. Chem. SOC. ( A ) ,1966, 1468.
( a ) E.g., A. Grace and P. Powell, J . Chem. SOC.( A ) , 1966, 673; ( b ) A. MelIer,
M. Wechsberg, and V. Gutmann, Monatsh., 1966,97,619,1163; ( c )J . M. Turner, J. Chem.
SOC. ( A ) ,1966,401,410,415; ( d ) K. Nagasawa, Inorg. Chem., 1966,5,442; (e)J. L. Boone
and G. W. Willcockson, ibid., p. 311; A. Meller and H. Egger, Monatsh., 1966, 97, 790.
1 4 0 J. H.Morris and P. G. Perkins, J. Chem. Soc. ( A ) ,1966, 576, 580; A. J. Downs
and J. H. Morris, Spectrochim. Acta, 1966, 22, 957; cf. Ann. Reports, 1965, 62, 360.
141 S. Trofimenko, J . Amer. Chem. SOC., 1966, 88, 1842.
K. W. Boddoker, S. G. Shore, and R. K. Bunting, J. Amer. Chem. SOC.,1966,
88, 4396.
143 F.Gr. Shorif and C. D. Schmulbach, Inorg. Chem., 1966, 5, 322.
144 ( a ) G. Hesse, H. Witte, and H. Haussleiter, Angew. Chem., Internat. Edn., 1966,
5, 723; G. Hesse, H. Witte, and W. Gulden, Tetrahedron Letters, 1966, 2707; ( b ) W.
Weber, J. W. Dawson, and K. Niedenzu, Irwrg. Chem., 1966, 5, 726; K. Niedenzu and
W. Weber, 2. Naturforsch., 1966, 21b, 811; K. Niedenzu and P. Fritz, 2. anorg. Chem.,
1965,340, 329.
146 N.E.Miller, M. D. Murphy, and D. L. Reznicek, Inorg. Chem., 1966, 5, 1832.
1413 V. B. Kravchenko, J. Strwt. Chem., 1965, 6, 76.
R. H. Cragg and M. F. Lappert, Organometallic Chem. Rev.,1966, 1, 43.
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DOWNS, EBSWORTH A N D T U R N E R : T H E TYPICAL ELEMENTS 155
appeared. Convenient syntheses of boroxine lPgU and trimethylboroxine 14gb

are described. Boroxine reacts rapidly14& with CO to give BH,,CO.
H2B203and &B@, have been identified in the gas-phase oxidation of
B,Hlo, B5H9, and BH,,CO; the short-lived species €330or H2BOH and
H,B02 (borane peroxide) are likely intermediate~.l4~Reports have appeared
of new derivatives of ring systems containing boron, carbon, and either
oxygen or sulphur, e.g., 1,3,2-dioxaborinan150° and 1,2-thiaboro1an;l50bthe
acceptor behaviour of some of these systems has been investigated.* 4- and
6-membered B-S ring compounds have been prepared l5la by the reaction of
H2S with trialkylamine-boranes ; 5-membered 1,3,44rithiadiborolan rings
result from the cleavage of polysulphur compounds (H2S,, S, disulphides) by
boron halides.151* Heating of 2,5-di-iodo-l,3,4-trithiadiborolan with BI,
causes ring-expansion with the formation of 2,4,6-tri-iodo-l,3,5-trithiatri-
borinan.151b 6-Membered B-P heterocyclic compounds substituted at
phosphorus have also been characterised.152
2,2’-Bipyridyl (bipy) forms para- and dia-magnetic chelate compounds
in which boronis stabilisedin unusual oxidation states,lL3e.g., (Me,N)2B(bipy).
The status of boronium salts is ambiguous; although the absorption spectra
of the diphenylboron and 9-borafluorene cations have been satisfactorily
interpreted,l540 and salts of the type @3un2B( amine),]+Cl- are reported,154*
attempts to characterise phenylboronium cations have been u n s u c ~ e s s f u l . ~ ~ ~
The CF, groups of the compounds CF3BBu2and CF3BF2suffer CF,-elimina-
tion only in the presence of catalysts;l55 in vacuo a t room temperature the
compounds are said to be “ stable for months.” The extent of B-C n-bonding
in vinylboranes has been gauged from spectroscopic 156u and molecular
orbital 166b considerations. The relative reactivities of competing B-X sites
with respect to organometallic compounds have been compared.l57
Recent surveys concern general features of metal borides 1580 and the
structural properties of boron and borides containing polyhedral B,, units.15gb
14* (a) L. Barton, F. A. Grimm, and R. F. Porter, Inorg. Chena., 1966, 6, 2076;
(b) M. W. Rathke and H. C. Brown, J . A m . Chem. Soc., 1966, 88, 2606; (c) S. K.
Wason and R. J. Porter, Inorg. Chem., 1966, 5, 161.
loS L. Barton, C. Perrin, and R. F. Porter, Inorg. Chm., 1966, 5, 1446.
lSo ( a )W. G. Woods and P. L. Strong, J . Amer. Chm. SOC.,1966, 88, 4667; (b) B. M.
Mikhailov, V. A. Dorokhov, and N. V. Mostovoi, Dokladp Chem., 1966, 166, 1114.
lS1 (a)J. A. Forstner and E. L. Muetterties, Inorg. Chem., 1966,5,164; (b) M. Schmidt
and W. Siebert, 2. anorg. Chem., 1966, 345, 87; M. Schmidt and W. Siebert, Angew.,
Chm., Internat. Edn., 1966, 5, 697.
lS2 R. I. Wagner and C. 0. Wilson, jun., Inorg. Chna., 1966, 5, 1009.
16s M. A. Kuck and G. Urry, J . Amer. Chem. Soc., 1966, 88,426.
154 ( a ) D. R. Armstrong and P. G. Perkins, J . Chem. SOC. ( A ) ,1966, 1026; (b) T. A.
Shchegoleva and 33. M. Mikheilov, Bull. Acad. Sci. U.S.S.R., 1965,693; (c) R. B. Moodie,
B. Ellul, and T. M. Connor, Chem. and Ind., 1966, 767.
lS6 T. D. Persons, J. M. Self, and L. H. Schaad, AD 620328, U.S. Oovt. Res. Develop.
Rept., 1965, 40, 38 (Chem. Abs., 1966, 64, 6674e).
16e (a) K. Niedenzu, J. W. Dawson, G. A. Neece, W. Sawodny, D. R. Squire, and
W. Weber, Inorg. Chtm., 1966,5,2161; K. Niedenzu and W. Sawodny, 2. anorg. C h . ,
1966, 844, 179; ( b ) D. R. Armstrong and P. G. Perkins, Thoretica China. Acta, 1966, 4,
69, 362.
1s7 M. F. Lappert and M. K. Majumdar, J . Organometallic C h n . , 1966, 6, 316.
lS* ( a ) R. Thompson, “ Borides: Their Chemistry and Applications,’’ Roy. Inst.
Chem. Lecture Ser., 1966; N. N. Greenwood, R. V. Parish, and P. Thornton, Q w r t .
Rev., 1966, 20, 441; (b) V. I. Matkovich, R. F. Giese, jun., and J. Economy, 2.K h t . ,
P
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156 INO RG ANIO CHEMISTRY
B,, icosahedra are the basic structural units of AIBl, (but not AIB1,, ap-
parently),15&whereas ScB12 and YB,, contain cubo-octahedral arrays of
boron atoms.158d A boride of potassium, KB,, has been prepared for the first
time. 158e
Aluminium. Reviews of general interest have appeared on complex
aluminohydr ides, 59a organoaluminium and aluminium-p hosphorus 1 6 1
compounds. Advances in aluminohydride chemistry have included the
synthesis of hexahydroaluminates M,Al€& (M = Li or Na) by two different
methods.159b The i.r. spectrum of the adduct LiAlH4,NEt3suggests 1 5 9 ~that
it is actually a complex of Et,N,AlH, and LiH. Clear, relatively stable solu-
tions of aluminium hydride,162prepared from 100% H2S0, and LiAlH, in
tetrahydrofuran, like related alurninohydrides, are useful reducing agents for
specific organic groups. LiAlH, reacts with B2H6 in ether solution giving as
products LiBH, and solvated AlH,(BH,),-, (n = 0, 1, 2, 3); 163a in tetra-
hydrofuran cleavage reactions lead to alkoxyaluminium compounds believed
to be the previously reported " triple metal hydrides." LiAlH, reduces
aluminium halides in a stepwise manner, giving hydridoaluminium halides,
which have been characterised as triethylamine adducts ; 1 6 X b these presum-
ably constitute the so-called " mixed hydride " reagents. Aluminium boro-
hydride complexes with Et,N [Et,N,Al(BH,),H] 164a and ethers (e.g.,
H2AlBH4,2THF) have been characterised ; in crystalline Me,N,Al( BH,),
a t low temperatures the aluminium is surrounded by a distorted pentagonal
bipyramidal array of ligands,l6& whereas at room temperature the con-
figuration is essentially tetrahedral.
A remarkable compound &,B(NMe,),Me,, formed from trimethyl-
aluminium and B2(NMe2),,may be the first example of a compound con-
taining Al-Al bonds; 1e5 (19) repreBents a possible structure. So-called
" isosteres " of tris(trimethylsily1)aminehave been prepared in which two of
the SiMe, groups are replaced by PMe, and MMe, (where M = Al, Ga, or
In),166 Properties of these compounds indicate the following order of acceptor
strengths : Me,Al> Me,Ga> Me31n. The Si-8-4 skeleton of Me,Si-8-AlEt,
(prepared from Me,SiF and AlEt,) 16' is isoelectronic not only with the
Al-F-A1 unit of [Et,Al-3'-AlEt,]- but with the Si-0-Xi unit of siloxanes,
1965, 122, 116; ( c ) G. Will, Nature, 1966, 212, 175; ( d ) V. I. Matkovich, J. Economy,
R. F. Giese, jun., and R. Barrett, Acta Cryst., 1965, 19, 1056; ( e ) R. Naslain and J.
gtourneau, Compt. rend., Xer. C, 1966, 263, 484.
159 ( a ) E. C . Ashby, Adv. Inorg. Chem. Rudiochem., 1966, 8, 2 8 3 ; ( 6 ) E. C. Ashby
and P. Kobetz, Inorg. Chew., 1966, 5, 1615; R. Ehrlich, A. R. Young, 11, G. Rice, J.
Dvorak, P. Shapiro, and H. F. Smith, J . Amer. Chem.Xoc., 1966,88, 858; ( c ) R. Ehrlich
and G. Rice, Inorg. Chem., 1966, 5, 1284.
160 R. Koster and P. Binger, Adv. Inorg. Chem. Radiochem., 1965, 7 , 263.
l G 1 G. Fritz, Angew. Chem., Internat. Edn., 1966, 5, 53.
l e aH. C. Brown, P. M. Weissmm, and N. M. Yoon, J. Amer. Chem. SOC., 1966, 88,
1458; H. C. Brown and N. M. Yoon, ibid., p. 1464.
1 6 s ( a )E. C . Ashby and W. E. Foster, J . A m r . Ohem. Soc., 1966, 88, 3248; (b) E. C.
Ashby and J. Prather, ibid., p. 729.
lti4 (a)R . Ehrlich and A. R. Young, 11, J. Inorg. Nuclear Chem., 1966, 28, 670;
(b) H. Noth and H. Suchy, J . Orgunometallic Chem., 1966,5, 197; ( c ) N. A. Bailey, P. H.
Bird,and M. C . H. Wallbridge, Chem. Comna., 1966, 286.
1 6 5 E. P. Schram, Inorg. Chem., 1966, 5, 1291.
166 H. Schmidbaur and W. Wolfsberger, A.ngew. Chem., Internat. Edn., 1966, 5, 312.
1 6 7 H. Schmidbaur and H. F. Klein, Angew. C h . ,Internat. Ed%, 1966,5,726.
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DOWNS, EBSWORTH AND T U R N E R : T H E T Y P I C A L E L E M E N T S 157
and is probably linear or nearly so. A ring structure with Al-F-Al bonding
is indicated for diethylaluminium fluoride,l**which is tetrameric in benzene
solution. Dialkylaluminium cyanides (Me,AlCN and Et,AlCN) lSgO and
azides (Et2AlN3)lSgbare also associated under normal conditions, with

degrees of aggregationranging from 3 to 8. Reports of new organoalllminium
compounds relate, inter alia, to 5-membered Al-C heterocycles,1700
aluminium-methylene compounds Y2Al-CH,*AlY, (Y = C1 or Et),l7M
alkali diethylalumino-aromatic complexes,l7~and alkyl(organosily1amino)-
aluminium deri~atives.170~Insertion of CH, occurs 170ewhen diazomethane
reacts with organoalanes, a process in which aluminium-ylides (R,Al-.CH,+)
may well be intermediates. 1 : 1 Complexes of CpzWH2 and Cp,ReH
(Cp= n-C5H5) with m e , (but not with BMe, or GaMe,) have been
is01ated.l'~
/Al \ yo\
0yo- Si,R3 MeZSi

I
SiMel
I
I 1
Me2Si SiMez (2')
\o'
The molecules of some dialkylaluminium alkoxides contain 4- or 6-
membered Al-0 rings, according to spectroscopic premises ;172s 173a
4-membered rings also form the basis of several newly characterised
aluminosiloxanes (structure XX where X = Me, R = Me;173uX = Me,
R = Ph;173a X = Br, R = Me;173b X = Me, R = H 17%). A compound
C,H,,A13Br50,Si,, formed by the reaction of octamethylcyclotetrasiloxane
with aluminium bromide or trimethylsiloxyaluminium dibromide, has the
structure (21) with a polycyclic system centred on a single 5-co-ordinate
aluminium at0rn.l7~~ Sublimation of the adduct &(NO3),,N.& obtained
from Al(N0,),,9Hz0 and N205, gives anhydrous &(NO,),, from which salts
of the [Al(NO,),]- anion have been prepared.l7* Of the two ions identified
A. W. Laubengayer and G. F. Lengnick, Inorg. Chem., 1966, 5, 603.
16@ ( a ) R . Ehrlich and A. R. Young, 11, J . Inorg. Nuclear Chem., 1966, 28, 674;
( 6 ) K. Dehnicke, J. Striihle, D. Seybold, and J. Miiller, J . Organometallic Chm., 1966,
6, 298.
1 7 0 ( a )J. J. Eisch and W. C. Kaska,J . Amer. Chena.rSoc., 1966,88,2976; H. Lehmkuhl,
Angew. Chem., Internat. Edn., 1966, 5, 663; (b) H. Lehmkuhl and R. Schafer, Tetra-
hedron Letters, 1966, 2315; ( c ) H. Lehmlruhl, Tetrahedron Letters, 1966, 2811, 2817;
( d ) D. Ya. Zhinkjn, G. K. Korneeva, N. N. Korneev, and M. V. Sobolevskii, J . Gem
Chem. (U.S.S.R.), 1966, 36, 360; (e) H. Hoberg, Annalen, 1966, 695, 1.
171 H. Brunner, P. C. Wailes, and H. D. Kaesz, Inorg. Nuclear Chem. Letters, 1965,
1, 125.
1 7 R. ~ Tarao, Bull. Chem. SOC. Japan, 1966, 39, 7 2 5 , 2126.
17* ( a )H. Schmidbaur and F. Schindler, Chem. Ber., 1966,99,2178; ( b )M. Bonamico,
G. Dessy, and C. Ercolani, Chem. Comm., 1966, 24; ( c ) J. F. Salmon, S. J. Evers, and
E. C . Evers, J . Inorg. Nuclear Chem., 1966, 28, 2787; ( d ) M. Bonamico, Chem. Comm.,
1966, 135; C. Ercolani, A. Camilli, and G. Sartori, J . Chem. Soc. ( A ) , 1966, 606.
C. C. Addison, P. M. Boorman, and N. Logan, J . Chem. SOC.( A ) ,1966, 1434.
View Article Online
by the vibrational spectra of alkaline aluminate solution^,^^^ the one pre-

dominating at pH>13isA102- (withDwhsymmetry),whilst that predominat-
ing at pH 8-12 is either square-planar Az(OH),- or, more likely, a polymeric
species built up from &(OH), octahedra.

Gallium, Indium, and Thallium. A new monograph deals with the
chemistry of gallium.176 The short-lived cations TIZ+and T1,+ have been
identified in aqueous solution by pulse radiolysis.177 Compounds containing
metal-metal bonds include the novel tetracarbonylcobalt derivatives, e.g.,
X,M[CO(CO),]~-,, (X = halogen; M = Gay In, or T1) l7sU resulting from
halide displacement or insertion reactions of tetracarbonylcobalt species, and
T1(SiEtJ3 and T1(GeEt3)3.17gbThe crystal structure of the room-temperature
modification of InCl implies 17& a t least incipient metal-cluster formation,
l151n n.m.r. spectra of aqueous solutions of indium compounds afford
information 179 about complex-formationand exchange processes. Relative
donor strengths with respect to GaH3 have been assessed qualitatively by
displacement reactions ; intramolecular hydrogen-elimination from the
adducts Me2n!tE€,GaH3(M = N or P) gives Me2MGaH2,of which the di-
methylamino-compoundis dimeric in benzene, but apparently monomeric in
the gas phase.lg00 The H-Ga bond of HGaCl, adds across double bonds,
giving organogallium derivatives (" hydrogallination ").1SOb
Four-membered G e O and In-0 rings analogous to XX constitute the
framework of a number of compounds of the type [X,M-0-MR,], (where
M = Ga or In; X = Me or C1; M = C, Si, or Ge; R = Me or Ph),1730,l g l a #
formed, for example, by the reaction of trialkyl-galliumor -indium etherates
with triorganosilanols. Organogallium dihalides are conveniently prepared
by the reaction of organosilanes or -germanes with gallium halides.l g l b
Electrical properties of In-InC1, melts support 1*2a the existence of InC1,
In2Cl3, and InCl,, of which only the InCl melt contains simple ions. Vi-
brational spectra,of gallium tri-chloride, -bromide, and -iodide comply with a
dimeric molecular structure in the solid and liquid phases.182b The prepara-
tion and properties of oxyhalides of gallium and indium,lg2dof the
thermally stable thallium compounds Tl,SCl, and T1,SeCl,,1s2B and of
anionic In-F complexes ls2f are described.
A variety of adducts of indium(m) and thallium(rn) halides has been
176 L. A. Carreira, V. A. Maroni, J. W. Swaine, jun., and R. C. Plumb, J . Chem.
Phys., 1966, 45, 2216.
170 I. A. Sheka, I. S. Chaus, and T. T. Mityureva, " The Chemistry of Gallium "
(Monograph 6; Topics in Inorganio and Generd Chemistry), Elsevier, 1966.
I f 7B. Cercek, M. Ebert, and A. J. Swallow, J . Chem. SOC. ( A ) , 1966, 612.
178 (a)D. J. Patmore and W. A. G. Graham, Inorg. Chem., 1966, 5, 1586; ( b ) N. S.
Vyazankin, E. V. Mitrofmova, 0. A. Kruglaya, and G. A. Razuvmv, J . Qen. Chem.
(U.S.S.R.),1966, 36, 166; (c) J. M. Van den Berg, Actu C ~ y s t . ,1966, 20, 905.
179 T. H. Cannon and R. E. Richards, Tram. P u r d u y SOC.,1966,62, 1378.
l80 (a)N. N. Greenwood, E. J. F. Rosa, and A. Storr, J . Chem. SOC. ( A ) ,1966, 706;
( b ) H. Schmidbaur and H. F. Klein, Angew. Chem., Internat. Edn., 1966, 5, 312.
lE1 (a) H. Schmidbaur and B. h e r , Angew. Chm., Inte4.nat. Edn., 1966, 5, 313;
(b) H. Schmidbaur and W. Findeiss, Chem. Ber., 1966,99,2187.
( a )V . N. Fadeev and P. I. Fedorov, R w s . J . Inmg. Chem., 1965, 10, 7 8 8 ; (b) A.
Balls, A. J. Downs, N. N. Greenwood, and B. P. Straughan, Trans. Furaduy SOC.,1966,
62, 521; (c) F. M. Brewer, P. L. Goggin and G. S. Reddy, J . Inorg. Nuclear Chem.,
1966, 28, 361; ( d ) P. I,.Goggin, I. J. M c C o h , and R. Shore, J . Chem. SOC.( A ) , 1966,
1004; ( e ) V. I. Rigin and S. S. Katsanov, Russ. J . Inorg. Chem., 1965, 10,950; (f)E. N.
Deichman and L. S. Krysina, ibid., p. 256.
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D O W N S , E B S W O R T H A N D T U R N E R : THE TYPICAL ELEMENTS 159
characterised.183u Physical properties, such as conductivities in non-
aqueous solution and i.r. spectra, form the basis of assignments to either
molecular (e.g., GaX,,L, where X = C1, Br, I; L = unidentate base) or
ionic (e.g. [T1(pyridine),C1,]+~Cl4]-)structures for these and similar com-

plexe~.~83~, b Relative donor and acceptor strengths, vix., N > S > 0 and
GaCl, > GaBr, > GaI,, based on thermochemical and n.m.r. measurements
on some 1 : 1 gallium trihalide adducts, are related 18% to steric and polari-
sability effects. Spectroscopic results suggest that the C-T1-C skeleton
of dialkylthallium cations is linear when coordinated by oxygen donors but
bent when co-ordinated by pyridine.
Group IV.-Ca&n. The CF, radical is pyramidal in thevapour phase1g4a
and in matrices,1g4bin contrast to the planar CH,; the angle lg5in CF, is
104.9". Methods of making graphitic oxide have been compared and im-
proved; carbon grains react with incandescencewith NF,in a Ni tube 186b
a t 150",and an explosion occurred when activated charcoal was treated with
NF, at low temperature. Equimolar adducts of R&oF and MF', (M = P,
As, Sb) have been prepared, which are volatile and appear to change from
molecular to ionic forms a t low temperatures;1*7 CCI, and Bu4NC1 give a
yellow solid adduct, formulated 188 as containing CCl,-. The heat of forma-
tion of t h i o c y a n ~ g e n and ~ values 1 8 g b for HX (X = NCO, NCS,
, ~ ~ ~pKu
NCSe, NNN), have been measured. The action of HC1 on NaOCN a t -80"
gives lgoU HNCO containing ca. 3% HOCN; the infrared spectrum of gaseous
fulminic acid indicates 190b that the H is bound to C. Carbonyl isocyanate
has been made by the thermal decomposition of trichloroisocyanuricacid ;l9lu
the action of boiling CC1, on (SbC14N3)2gives 191b[C(N,),]+sbC16-.
Silicon. The reactions of elementary silicon have been reviewed.lQ2
Photolysis of silyl azide at 4 ° K gives a species identified by infrared spectro-
scopy lQSUas HNSi; the e.s.r. spectrum of the SiH, radical, formed in a Kr
matrix a t 4"K, indicates that the species is ~yramidal,l93~ as (probably) are
GeH, and SnH,. The lower hydrides produced by the action of aqueous,
ethanolic, or ammoniacal acids on CaM or Ca,M (M = Si or Ge) are of
formulae SiR,.,, and GeH,.9-1.2; the reported formation of MH, has not
(a)A. J. Carty and D. G. Tuck, J . Chem. Xoc. ( A ) ,1966, 1081; B. F. G. Johnson
and R. A. Walton, Inorg. Chem., 1966, 5, 49; ( b ) W. R. McWhinnie, J . Chem. SOC.( A ) ,
1966, 889; N. N. Greenwood, T. S. Srivastava, and B. P. Straughan, ibid., p. 699;
( c ) N. N. Greenwood and T. S. Srivastava, ibid., pp. 267, 270, 703; ( d ) G. D. Shier and
It. S. Drago, J . OrganmetaZlic Chern., 1966, 5, 330.
lS4 ( a ) G. A. Carlson and G. C. Pimentel, J . Chem. Phys., 1966, 44, 4053; ( b ) D. E.
Milligan, M. E. Jacox, and J. J. Corneford, ibid., p . 4058.
F . X. Powell and D. R. Lide, J . Chem. P h y . , 1966, 45, 1067.
186 ( a ) H. P. Boehm and W. Scholz, Annalen, 1966, 691, 1; (b) J. Massonne and R.
Holst, Angew. Chem., Internat. Ed%., 1966, 5, 317.
E. Lindner and H. Kranz, Clzem. Ber., 1966, 99, 3800.
l B S D. H. McDaniel and R. M. Dieters, J . Amer. Chem. SOC., 1966, 88, 2607.
(a)C. E. Vanderzee and A. S. Quist, Inorg. Chem., 1966, 5, 1238; ( b ) J. H .
Boughton and R. N. Koller, J . Inorg. Nuclear Chem., 1966, 28, 2851.
l g o( a ) N. Groving and A. Holm, Acta Chem. Xcand., 1965, 19, 1768; ( b ) W. Beck
and I<. Feldl, Angew. Chem., Internat. Edn., 1966, 5, 722.
lg1 (a)E. Nachbaur, Monatsh., 1966,97,361; (b) U. Muller and R. Dehnicke, Angew.
Chem., Internat. Edn., 1966, 5, 841.
l g aE. Bonitz, Angew. Chem., Internat. Edn., 1966, 5, 462.
lea(a)J. F. Ogilvie and S. Cradoclr, Chem. Conam., 1966, 364; (b) R. L.Morehouse,
J. J. Christiansen, and W. Gordy, J . C h m . Phys., 1966, 45, 1751.
View Article Online
160 I N O R Q A N I C CHPJMISTBY
been confirmed.104 In SiF,, the microwave spectrum leads to a bond anglelO5Q

of 100'59'; the reactions of the species in matrices at low temperatures lQSb
and with unsaturated systemsl0& have been investigated. The Me,Si
radical, generated by the thermal decomposition of (Me,Si),Hg, extracts

oxygen or halogen atoms from organic solvent^.^^^ The relationship between
(p4)n-bonding and bond angles in (SiH&N and related species has been
discus~ed.~~7 Microwave spectroscopy shows that the &eleton of SiH3NC0
is linear;lOsaelectron diffraction, however, indicates that Me,SiNCX (X = 0
or S) is bent at N.lOsbThe shifts to higher energies in the U.V. spectra of
(SiH,),Z (Z = Cl, 0, N) when compared with (CH3),Z are consistent with
(p+d) n-bonding in the former species.lo9 The large shifts200a to lower
energies in the (n-n*) transitions of R,MCOR as M changes from C to Si,
Ge, or Sn have been put down largely to inductive electron release, rather
than to n-interactions, and evidence as to the basicities of the ketones
concerned is cited in support.200bIn Pt(@complexes the exceptionally low
values forv(Pt-X) (X =C1 or Br) tram to R3Sor R3Gehave been interpreted
as indicating that Si has the largest known trans effect of inductive origin.
Additivity parameters for heats of formation of organosilicon compounds
have been discussed,202and values for a number of bond energies 203a and
bond dissociation energies 203b involving Si, Ge, and Sn have been reported.
Controversy continues 204a over the value of D(Si-Si) in Me,Si,. In
SiH3GeH3,mass spectrometry 204b leads to a value for D(Si-Ge) of 99.9
kcal., whilst a thermochernical method 20gc gives E(Si-Go) as 42.5 kcal.
Exchange reactions at Si and Ge have been extensively studied;205"exchange
involves halogen 205b and pseudohalogen 205c groups, oxygen, nitrogen,20Sd
and (in the presence of AlC1,) methyl groups.2o5s
Silylpotassium reacts with monochloro-N-dialkylaminoboranes and trial-
19* 9. Royen and C. Rockthchel, 2.anorg. C h . , 1966, 346, 279.
195 ( a ) V. M. Rao, R. F. Curl, P. L. Timms, and J. L. Margrave, J . Chem. Phys.,
1965,43, 2557; ( b ) J. M. Bassler, P. L. Timms, and J. L. Margrave, Inorg. Chm., 1966,
5,729; (c)P. L. Timms, D. D. Stump, R. A. Kent, and J. L. Margrave, J . Amer. Cham.
Soc., 1966, 88, 940; J. C. Thompson, J. L. Margrave, and P. L. Timma, Chem. Comm.,
1966, 566.
lg6 A. G. Beaumont, C. Eaborn, R. A. Jackson, and A. W. Walsingham, J . Organo-
metallic Chern., 1966, 6, 297.
lo7 E. A. V. Ebsworth, Chem. Comm., 1966,530; E. W. Randall and J. J. Zuckennan,
ibid., p. 732.
lQ8 ( a ) M. C. L. Gerry, J. C. Thompson, and T. M. Sugden, Nature, 1966, 211, 846;
(b) K. Kimura, IF. Katada, and S. H. Bauer, J . Amer. Chm.SOC.,1966, 88, 416.
199 S. Bell and A. D. Walsh, Trans. Faraday SOC.,1966, 62, 3005.
( a ) G. J. D. Peddle, J . Orgametallic Chem., 1966, 5, 486; ( b ) K. C. Yates and
F. Agolini, Canad. J . Chem., 1966, 44, 2229.
801 J. Chatt, C. Eaborn, and S. Ibekwe, Chem. Comm., 1966, 700.
2 0 2 H. E. O'Neal and M. A. Ring, Inorg. Chem., 1966, 5, 435.
203 ( a ) A. Beezer and C. T. Mortimer, J . Chem. SOC. ( A ) ,1966, 514; (b) G. W. Hess,
F. W. Lampe, and A. L. Yergey, Ann. New York Acad. Sci.,1966, 186, 106.
3 0 4 ( a )J. A. Connor, G. Finney, G. J. Leigh, R. N. Haszeldine, P. J. Robinson, R. D.
Sedgwick, and R. F. Simmons, C h m . Comm., 1966, 178; I. M. T. Davidson and I. L.
Stephenson, ibid., p. 746; ( b ) F. E. SaaKeld and H. J. Svec, J . Phys. Chem., 1966, 70,
1753; (c) S. R. Gunn and J. H. Kindsvater, ibid., p. 1751.
2 0 5 ( a ) K. Moedritzer, Orgartometatiic Chem. Rev., 1966, 1, 179; ( b ) J. R. van Wazer,
K. Moedritzer, and L. C. D. Groenweghe, J . OrganometallicC h . , 1966, 5, 420; (c) K.
Moedritzer and J. R. van Wazer, {bid., 1966,6,242; ( d ) J. F. Klebe, H. Finkbeher, and
D. M. White, J . Amer. Chem. SOC.,1966, 88, 3390; (e) H. Sakurai, K. Tomhaga, T.
Watanabe, and M. Kumada, Tetrahedron Letters, 1966, 5493.
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D O W N S , EBSWORTH A N D T U R N E R : T H E TYPICAL ELEMENTS 161
kylamine adducts of monochloroboranesto give silyl-N-dialkylaminoboranes
[e.g., SiH,B(NMe,),] or adducts of silylboranes [e.g., SiH3BH2,NEt3] ; with
chloroboranes, or with dichloro-N-dialkylaminoboranes,unstable species are
formed.206a Triphenylsilyl-lithium reacts with chloro-N-dialkylamino-

boranes to give triphenylsilyl-N-dialkylaminoboranes, which are also obtained
from R,SiCl, (R2N),BC1, and potassium; silylboranes were not obtained
from reactions with B-alkyl-chloroboranes.206b Bis(triphenylsily1)mer-
cury,2060bis(triethylsilyl)cadmium,206dand tris(triethylsily1)thallium and its
germyl analogue 178b have been prepared. Details of the determination of the
absolute configuration of l-naphthylphenylmethylsilaneand of its fluoride
have been gi~en.~07Ethyl-lithium reacts with disilane to give ethyldisi-
laneY2Osa which reacts with KH, forming EtSiH, and SiH4;the S i - S i bond
in disilane breaks in the presence of LiX (X C1, Br,I).20sa The chemistry
I=
of compounds containing M-M bonds (M = Si, Ge, Sn, Pb) has been
reviewed;209the e.8.r. spectrum of cyclo-Me@,- shows that the protons, the
carbon atoms, and the silicon atoms comprise equivalent sets ;210 methylated
linear polysilanes have been prepared 211a up to Me2,Si12, and methods of
preparing species containinghighly branched Si chains have been described.2llb
Ph2Si -SiPhz Ph S'- SiPhz

I
Ph2Si -SiPhz
I 21' I
Ph2Si SiPh;!
\ /
(22) Q (23)
The compound (22) reacts with lithium followed by QC1, (Q = S, PhP,

Ph,Si, Ph2Ge, Ph,Sn) giving 212 the heterocyclic compounds (23). The
elusive (SiH,),NH has been prepared from ammonia and Ph2NSiH3,and some
of its reactions have been studied;21s the action of ammonia on (Si€€,),N
gives 214 (SiH3NSiHZ),.Bis(trimethylsily1)amine forms 1 : 1 adducts with
AlC1, and GaC1, that are associated in benzene, but the adduct (Me,Si),N,AlCl,
is partly dissociated in that solvent into its components.21KuStable adducts
of SnCl, with (Me,SiNH),, (Me,Si)&F€,and Me3SiNMezhave been~repared.~15~
The action of SOCI, on (Me,Si),N gives 216 Me,SiNSO. Dimethylamine
806 ( a ) E. Amberger and R. Romer, 2. unorg. Chem., 1966, 345, 1 ; (b) H. Noth and
G. Hollerer, Chem. Ber., 1966, 99, 2197; ( c ) R. A. Jackson, Chem. Comm., 1966, 827;
( d ) N. S. Vyazankin, G. A. Razuvaev, and V. T. Bychkov, J . e n . Chem. (U.S.S.R.),
1965, 35, 394.
a07 Y. Okaya and T. Ashida, Acta Cryst., 1966, 20,461.
( a )W. J. Bolduc and M. A. Ring, J . OrganometaZZic Chem., 1966, 6, 202; ( b ) R. C.
Kennedy, L. P. Freeman, A. P. Fox, and M. A. Ring, J . Inorg. Nuclear Chem., 1966,
28, 1373.
aos H. Gilman, W. H. Atwell, and F. K. Cartledge, Adv. Organornetdic Chem., 1966,
4, 1.
alo G. R. Husk and R. West, J . Amer. C h m . Soc., 1965, 87, 3993.
*11 (a)M. Kumada, M. Ishikawa,and S. Maeda, J . Organometa& Chem., 1966, 5,
120; ( b ) H. Gilman and R. L. Harrell, ibid., p. 199.
al* E. Hengge and U. Brychey, Nonut&., 1966, 97, 1309.
B. J. Aylett and M. J. Hakim, Inorg. Chm . , 1966, 5, 167.
%14 R. L. Wells and R. Schaeffer, J . Amer. Chem. SOC.,1966, 88, 37.
p16 ( a ) , N. Wiberg and K. H. Schmid, 2. unorg. C h m . , 1966, 345, 93; ( b ) M. F.
Lappert and G. Srivastava, Inorg. Nuclear C h m . Letters, 1965,1, 63.
I1@ 0. J. Scherer and P. Hornig, Angew. Chem., Internat. Edn., 1966, 5, 729.
View Article Online
reacts 217 with Si2C1, to form (Me,N),Si2; the compound Ph,SXElCl is

formed 21g as an intermediate in the production of Ph,SiNC12 from Ph,SiNH,
and Me3COC1. Interest in silyl derivatives of hydrazine is maintained; 21Q0
the structures of the isomeric hydrazine derivatives (Me,Si),N,H, have been

reassigned on the basis of spectroscopic evidence, and several new species
(R3Si)2N2Hahave been prepared.21Qb Amines containing SiF, groups
have been made from the amine adducts of SiF,, and some of their properties
have been reported.220 Triphenylsilyl azide reacts with PhpP2to give221
Ph,SiN*PPh,*PPh,*NSiPh,; the compound Me,SmPMe,, made from
Me,SiN3 and PMe,, forms 1: 1 adducts1G6with MMe, (M = Al, Gay In).
The series of compounds 222 [Me,Si(Me)N],IMMe,-, (n = 1-43;M = As, Sb,
Bi) has been made from Me,SiN(Me)Li and Me,,MX, (X = C1 or Br). The
chemistry of SiN heterocycles has been reviewed;223aspecies containing the
ring system (24) have been synthesized 223b from R,”SiCl*SiR,”Cl and
R,Si(NLiR’)2.
Si
R’ ‘R‘ (2s)
The formation and reactions of Si-P compounds have been discussed;Is1

silylphosphinegives an adduct with BE‘,a t -134”that decomposes a t higher
temperatures, SiH3F’and (SiR,),P being amongthe products.224~AlkaIi metal
mercaptides replace R,Si or R3Sngroups bound to phosphorus partly or com-
pletely by RS gr0ups;2~4~ Me,SiP(SEt), has been made from (Me,Si),P and
(SEt),. The compounds (Et3M)3M(M = Si, Ge, Sn; M‘ = Sb, Bi) have been
prepared 225 from Et,MH and Et,M’. The compound Me,SiAsMe, gives wb
Me,AsC(S)S-SiMe, with CS,, and forms a 1 : 1 adduct with HBr.
The action of chlorine on R,SiONa gives R,SiOCI, and not (as reported) a
a17E. Wiberg, 0. Stecher, and A. Neumaier, I m T g . Nuclear Chem. Letters, 1965,1,33.
218P. Bekiaroglou, 2.anorg. Chern., 1966, 345, 290.
21a( a )U.Wannagat, G . Schreher, 0. Brandstiitter, and 1\6. Peach, Monatsh., 1965,
98,1902; F. Hofler and U. Wannagat, ibid., 1966,97,1598; ( b )U. Wannagat, F. Hbfler,
and H. Biirger, ibid., 1965, 96, 2038; R. West, M. Ishikawa, and R. E. Bailey, J . Amer.
Chem. Soc., 1966, 88,4648.
azo M. Allan, B. J. Aylett and I. A. Ellis, Inorg. Nzcckar C h m . Letters, 1966, 2,
261; Chem. and Ind., 1966, 1417.
zal K. L.Paciorek and R. H. Kratzer, J . Org. Chem., 1966, 81, 2426.
22a 0. J. Scherer, P. Hornig, and M. Schmidt, J . Organometdlic Chem., 1966, 6,269.
2z3 ( a ) W. Fink, Angew. Chem., Internat. Edn., 1966, 5, 760; (b) U. Wannagat and
0. Brandstiitter, Monatsh., 1966, 97, 1352.
2 2 4 ( a ) C. R. Russ and A. G. M a c D i d d , Angew. Chem., Internat. Edn., 1966, 6,
418 ; ( b )A. B. Brucker, L. D. Balmhova, and L. Z. Soborovskii,J . Gen. Chem. (U.S.S.R.),
1966, 36, 79.
N. 8. Vyazankin, G. A. Razuvaev, 0. A. Kruglaya, and G. S. Semchikova,
J . Organometallic Chem., 1966, 6, 474.
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D O W N S , E B S W O R T H AND T U R N E R : T H E T Y P I C A L E L E M E N T S 163
peroxy-~pecies;~~0~ the hypochlorite adds to Ph,As and Ph,Sb. The dimers
(Me,SiOAlBr,), and (Me,SiOAlMe,), contain the expected planar 4-mem-
bered Al-0-Si ring structures. Sodium trimethylsilanolate reacts with
Me2AuBrto give 2~ Me,SiOAUMe,. Silanols react 227a with perfluoracetone,

giving (CF3),C( OH)OSiR,. In the presence of HgI,, CH,:C(OMe)OSiEt,
rearranges 2278 to Et,SiCH2C02Me. The properties of Si-S compounds have
been reviewed;228usilicon is displaced from (25) by the halides of metal-
loids 228b such as ByP, As, Sb, and Sn. A compound containing sulphur bound
to an asymmetric silicon centre has been prepared, and some of its reactions
investigated.22& Compounds of formulae (RSi),M, (M = S or Se), believed
to have adamantane-like structures, have been made from RSiCl, and H2M;
with RSnCl,, however, products (RSn),S, are formed.229 Phase studies 230
indicate that the only binary Si-Te species formed in the solid state is Si,Te,.
Refluxing of Ph,Si with Co2(CO)8gives [(CO),Co,Si],; compounds con-
taining Me,Si and Me,Ge groups bound t o platinum have been ~repared.231~
The electrochemistry of Ph,M derivatives (M = Si, Ge, Sn) has been in-
vestigated.la, The formation and properties of organofluorosilicates has
been reviewed ;232a aqueous SbF, reacts with organofluorosilicates 2~ to
form R,Sb. Methylchlorosilanes form adducts with HCl and tetraalkylam-
monium halides. 255 Trimethylamine and HCF2CF2SiH,give an equimolar
adduct, liquid at room temperature, that is believed to contain 5-co-ordinated
silicon.234
Germanium. In the crystal, GeF, is a fluorine-bridged chain polymer,
~ ~ solubility of GeO, in
with weak fluorine bridges between ~ h a i n s . 2 The
acids and bases has been st~died;2~6U the overall hydrolysis constant of
GeXe2- to Ge02(hex.)is given by log K288= -25-8&-0*3,and the hydrolytic
equilibria have been discus~ed.2~~~ Complex compounds of germanium, and
the state of germanium in solution, have been reviewed.23M The action of
conc. HIO, or HIO, on GeO, gives basic Ge(Iv) iodate or p e r i ~ d a t e .In ~~~~
( a )J. Dahlmann, A. Rieche, and L. Austenat, Angew. Chem., Internat. Edn.,

1966, 5,727; ( b ) H. Schmidhaur and M. Bergfeld, I m g . Chem., 1966, 5, 2069.
827 (a)A. F. Janzen and C. J. Willis, Canad.J . Chem., 1966,44,745; (b) I. F. Lutsenko,
Yu. I. Baukov, G. S. Burlachenko, and B. N. Khasapov, J. Organometallic Chem.,
1966, 5, 20.
(a) A. Haas, Angew. Chem., Internat. Edn., 1965, 4, 1014; (b) E. W. Abel, D. A.
Armitage, and R. P. Bush, J . Cltem. SOC.,1965, 7098; ( c ) L. H. Sommer and J. McLick,
J . Amer. C h m . SOC.,1966, 88, 5359.
saQ J. A. Forstner and E. L. Muetterties, Inorg. Chem., 1966, 5, 552.
8ao L. G. Bailey, J . Phys. and Chem. Solids, 1966,27, 1593.
281 (a) S. F. A. Kettle and I. A. Khan, J . OrganometaWic Chern., 1966, 5, 588; ( b ) F.
Clockling and K. A. Hooton, C h . Comm., 1966, 218.
a32 ( a ) R. Miiller, OrganometaEliG Chem. Rev., 1966, 1 , 359; ( b ) 33. Miiller and C.
Dathe, Chem. Ber., 1966, 99, 1609.
ass N. M. Alpatova, Yu. M. Kessler, and A. I. Gorbmev, R w s . J . Inorg. Chem.,
1965, 10, 854.
a 3 4 D. I. Cook, R. Fields, M. Green, R. N. Haszeldine, B. R. Iles, A. Jones, and
M. J. Newlands, J . Chem. SOC.( A ) ,1966, 887.
a s 6 J. Trotter, M. Akhtar, and N. Bartlett, J . Chem. SOC.( A ) ,1966, 30.
*3* (a)E. A. Knyazev, I. A. Kakovskii, and Yu. B. Icholmanskikh, R w s . J . I w g .
Chem., 1965, 10, 1464; L. N. Shigina and V. M. Andrew, ibid., 1966, 11, 469; (b! I. Q.
Ryss and N. F. Kulish, ibid., 1965,10,996; ( c ) V . A. Nazarenko and A. M. hdrianov,
R w s . Chena. Rev., 1965, 36, 547; (d) N. I. Lobanov, Rum. J . Inorg. Chem., 1966, 11,
238; (e) R. S. Tobias and S. Eutcheson, J . Orgametallic Chem., 1966, 6, 535.
View Article Online
water, Me,Ge2+ cations are not formed; the species present is identified by
Raman as Me,Ge(OH),. The heat of formation AH,02s8 of
of GeF, is found to be -284*37&0*15 kcal./mole by fluorine bomb calori-
m e t ~ y The ~ of an electric discharge on a mixture of GeH,, SiH,, and

. ~ ~action
Si,H, has led to the provisional identification of ten new hydrides by mass
spectrometry.23s The n.m.r. spectra of R,GeH,,, andR,GeH,-,- (n, = 0-3)
in liquid ammonia have been measured;23B it is deduced that GeH, is a much
stronger acid than Ph,GeH. The halides GeH,X and Ge,H,X (X = C1, Br)
have been prepared 240a from the hydrides and AgX; monogermane and
CF31give GeH,I when heated t0gether.240~ Organogermanium chemistry
has been r e v i e ~ e d , and ~ mass spectra of a number of organoger-
~ ~ l the
manium species have been determined.241b Some of the simpler con-
jugated dienes react with GeI, to form 5-membered ring species containing
GeI, gr0ups;~4~" treatment of the etherate of HGeX, with MeMgBr or MeLi
gives 2*2b Me(GeMe,),Me, (Me,Ge),, and (Me,Ge),. Hexaphenyldigermane
reacts with Sr and Ba in liquid ammonia to give (Ph,Ge),M (M = Sr, Ba);
the analogous zinc derivative has been made from Ph,GeNa and ZnC1,
in the same Some of the reactions of (Et,Ge),Cd have been
st~died.~43bSolutions of Ph4As+MC1,- (M = Ge, Sn) in CH,C1, react with
BX, (X = 3' or Cl) to precipitate 1 : 1 adducts formulated 7w as
-.
Ph4As+[X,BMCl,] Improvements in the direct synthesis of MeGe halides
have been described;244 details of the preparation and reactions of optically
active 1-naphthylphenylethylgermylcompounds have been given.245 In the
crystal, Me,GeCN has the normal cyanide structure ; in the Gem-Ge chains,
the Ge-N distances are not unusually short.246 The species R,Ge.GeR,Cl are
formed 247a from GeCl, and R,Ge, ; potassium in hexamethylphosphotria-
mide reacts with R,Ge2 to give high yields 247b of R,GeK. The action of
MH, (M = P, As) on Me,GeNMe2 or (Me,Ge),m gives (Me3Gc)3M,also
formed from Me,GeCl and Na,M in liquid ammonia;24SQPh,M derivatives
( M = Ge, Sn, Pb) of Ph,M"H,,, (M" = P, As, Sb) have been prepared.248b
It is deduced from the infrared spectra that the M& ' ' skeletons are pyra-
aa7 P. Gross, C. Hayman, and J. T. Bingham, Tram. Paraday SOC.,1966, 62, 2388.
238 T. D. Andrews and C. S. G. Phillips, J . Chem. Soc. ( A ) ,1966, 46.
T. Birchall and W. L. Jolly, Inorg. Chem., 1966, 5, 2177.
a 4 0 ( a ) K. M. Mackay, P. Robinson, E. J. Spanier, and A. G. MacDiarmid, J . I w q .
Nuclear Chem., 1966, 28, 1377; ( b ) J. E. GrifEths and A. L. Beach, Canad. J . CTLem.,
1966, 44, 1227.
241 (a)F. Glockling, Quart. Rev., 1966, 20, 45; ( b ) D. B. Chambers, F. Glockling,
J. R. C. Light, and 35. Weston, Chem. Comm., 1966, 281.
a 4 3 (a) P. Mazerolles and G. Manuel, BUZZ.SOC.chim. France, 1966, 327; (b) 0. M.
Nefedov and S. P. Kolnesikov, BdZ. Awd. Sci. U.S.S.R., 1966, 201.
B43 (a)E. Amberger, W. Stoeger, and R. Honigschmid-Grossich, Angew. Chi%.,
Internat. Edn., 1966,5,522; ( b ) N. S. Vyanzankin, G. A. Razuvaev, V. T. Bychkov, and
V. L. Zvezdin, Bull. Acad. Sci. U.S.S.R., 1966, 562.
244 K. Moedritzer, J . Organmetallic Chem., 1966,6,282; M. Wieber, C. D. Frohning,
and M. Schmidt, ibid., p. 427.
8 4 5 C. Eaborn, P. Simpson, and I. D. Varma, J . Chern. SOC. (A), 1966, 1133.
a 4 6 E. 0. Schlemper and D. Britton, I w g . Chem., 1966, 5 , 611.
E. J. Bulten and J. G . Noltes, TetraMron Letters, 1966, (a)p. 3471; (b) p. 4389.
3 4 8 ( a )I. Schumann and H. Blau, 2. Naturforsch., 1966,21b, 1105; ( b ) M. Schumann
and M. Schmidt, Inorg. Nuclear Chern. Letters, 1965, 1, 1 ; H. Schumann, P. Schwab,
snd M. Schmidt, ibid., 1966, 2, 309; (a) W. P. Neumann, B. Schneider, and R. Sommer,
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D O W N S , E B S W O R T H A N D T U R N E R : T H E T Y P I C A L ELEMENTS 165
midal. Compounds containing Ge bound to Sn or Pb have been obtained

from R,GeH and R3M(NMe2) (M = tin 24& or lead 248d). The compounds
(Et,M),BiEt 3--n (M = Ge or Sn) have been prepared.,4& Trialkylgermanols
react with gallium alkyls to give 181b dimeric R,GeOGaR,. Triphenylgermyl

peroxide249 has been made from Ph,GeBr and H,O,. The complex
(Et,P),Pd(GePh,), reacts 2Ma with H, under pressure at Z O O , giving
(Et,P),Pd(H)GePh,. The insertion of Ge(n) and Sn(n) halides into metal-
metal bonds has been further investigated.250b
Tin. Studies of e.m.f. in fused NaAlCl, indicate that there is a one-
electron reduction process for Sn and Pb.251 A 1 : 1 adduct 252a is formed
between (Q,PN), and SnC1, when Q = Me, but not when Q = Ph or C1. I n
aqueoussolution,complexesSn(0,CMe),(n-2)- have beenidentified (n= 1-3),
with polymeric species ;252bthe formation constants for polyphosphate com-
plexes of Sn(n) in water have been m e a ~ u r e d . ~The
~ ~ cformation and pro-
perties of organotin cations have been reviewed.253a The Siuence of the
nature of R upon the hydrolysis of R,Sn+ and R,Sn2+ has been investigated;
the species R2SnOH+tend t o d i m e r i ~ e . ~ Anodic
5 ~ ~ oxidation in methanol
gives Eo(SnMe3+/Me,SnSnMe,) as +0*14l v.254 Tetramethyltin forms
Me,SnHSO, and methane with concentrated H2S04, but Sn-C bonds in
Ph-Sn compounds are all broken ; alkyltin hydrogen sulphates and bis(hydro-
gen sulphates) are strong bases in that solvent, probably because of proto-
nati0n.~5~ Vibrational spectra indicate that (R,Sn),M (M = 0, S, Se) are
bent 256a at M, and (Me,Sn),M' (M' = N, P, As, Sb) are pyramidal 256b a t M .
The failure to observe quadrupole splitting in the Mossbauer spectra of a
number of asymmetrically substituted Sn(rv) derivatives 257a is still not
fully understood, though Mossbauer data for a wide range of tin compounds
have been reported ;257b there is evidence from Mossbauer spectroscopy 257c
that Sn(AlH,), is an intermediate in the reduction of SnCl, to SnH, by
LiAlH,. The type of product obtained from the addition of tin hydrides to
a/?-unsaturated ketones depends on the h ~ d r i d e . ~Very
5 ~ ~ reactive com-
Annalen, 1966, 692, 1; ( d ) W. P. Neumann and K. Kiihlein, Tetrahedron Letters, 1966,

3419; ( e )0. A. Kruglaya, N. S. Vyazankin, and G. A. Razuvaev,J. Qen. Chem. (U.S.S.R.),
1965, 35, 392.
24v R. L. Dannley and G. Farrant, J . Amer. Chem. SOC., 1966, 88, 627.
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( A ) ,1966,1241 ; (b) D. J. Patmore
and W. A. G. Graham, Imrg. Chem., 1966,5,1405.
251 T. C. F. Munday and J. D. Corbett, Inorg. Chem., 1966, 5, 1263.
2 5 2 (a) M. F. Lappert and G. Srivastava, J. Chem. SOC.( A ) , 1966, 210; ( b ) J. D.
Donaldson and J. F. Knifton, ibid., p. 332; (c) R. E. Mesmer and R. R . Irani, J. Inorg.
Nuclear Chem., 1966, 28, 493.
2S3 (a)R. S. Tobias, Organometall~ic Chem. Rev.,1966, 1, 93; (b) R. S. Tobias, H. N.
Farrar, M. B. Hughes, and B. A. Nevett, Inorg. Chem., 1966,5,2052.
2 5 4 G. Tagliavini and L. Doretti, Chem. Comm., 1966, 562.
R. J. Gillespie, R. Kapoor, and E. A. Robinson, Canud. J. Chem., 1966, 44, 1197.
2 5 6 (a)H. Kriegsmann, H. Hoffmann, and H. Giessler, 2. anorg. Chern., 1965, 341,
24; (b) R . E. Hester and K. Jones, Chem. Comm., 1966, 317.
2 5 7 (a)T. C. Gibb and N. N. Greenwood, J. Chem. SOC.( A ) ,1966, 43; R. H. Herber
and G. I. Parisi, Inorg. Chem., 1966, 5, 769; ( b ) J. W . Donaldson and B. J. Senior, J.
Chem. SOC.( A ) ,1966, 1796, 1798; D. Khristov, Tsv. Bouchev, and Kl. Burin, Compt.
rend. Acad. bulg. Sci., 1966, 19, 293; A. J. Bearden, H. S. Marsh, and J. J. Zuckerman,
Inorg. Chem., 1966, 5, 1260; (c) Z. Boutschev, D. Christov, Kl. Burin, and Iv. Mand-
zukov, 2. anorg. Chem., 1966, 347, 199.
2 5 8 (a) M. Pereyre and J. Valade, Compt. rend., 1965, 260, 581; A. J. Leusink and
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166 INORQANIC CHEMISTRY
pounds, useful as synthetic intermediates, are obtained from the unexpectedly

easy addition of Sn-H bonds to CN in alkylidenemalononitrile~.~5B* The
reaction between alkyltin hydrides and R,SnX (X = NR,, OR, OSnR,) or
related species 248c, 259a affords a means of forming Sn-Sn chains and rings,
and is an example of a general way of forming metal-metal bonds;25gbrings
up to (R,Sn), have been obtained 259c thus and by catalytic dehydrogenation
of R,SnH2. The properties of organic tin-nitrogen compounds have been
reviewed.26* Distannoxanes 261a react with H S C R to give R,SnC=-CR’;
with secondary amides NHR’COX there is a similar reaction, unless X $very
electronegative, when R,SnX is eliminated, but with primary amides
R,SnNCO is formed.261b Reactions between isocyanates and distannoxanes
have also been investigated.261c Compounds of the form (R,PS,)SnR’, and
(R,PS,),SnX, (X = C1, Br) have been obtained;262tin-sulphur bonds are
broken by HgCl,, CdCl,, CdBr,, K2PtC14,263and Hg(NPh*C02H)2,261b and
tin-selenium bonds 264 by BrMn(CO),. A number of compounds containing
Sn bound to transition metals have been reported.265 The n-acceptor pro-
perties of SnQ, (& = alkyl, aryl, CT) have been assessed in Q,Sn*Mn(CO),-
derivatives (by the CO stretching frequencies), and in nz- and
p-FC6H4Pt(PEt,),SnCl, (from the F chemical shift) ;266b the group-SnC1,
appears to be a strong n-acceptor. The role of solvent in relation to the
formation of adducts of tin(Iv) halides has been considered;267athe adduct
SnCl,,N,O, is formulated 267b as NO+(SnCl,NO,) -.
Compounds containing
(Me,SnX,)- and (Me,SnX4)2- (X = F, C1, Br) have been prepared;268Qthe
adduct 2,2’,2”-terpyridyl,2Me,SnC12 has been shown crystallographically to
contain the ions (Me,Sn,terpy)+ and (Me,SnCl,)-, the methyl groups in the
latter occupying equatorial positions of the trigonal bipyramid.26*b
Lead. The hydrolysis of Me,Pb2+ has been investigated;z69 some
associated species are formed, and Rnrna,n spectra indicate co-ordination of
J. C.Noltes, Tetrahedron Letters, 1966, 2221; ( b ) W. P.Neumann, R. Sommer, and E.

Muller, Angew. Chem., Internat. Edn., 1966, 5, 514; R. Sommer and W. P. Neumann,
ibid., p. 516.
2 5 9 ( a ) R. Sommer, B. Schneider, and W. P. Noumann, Aniaalen, 1966, 692, 12;
( 5 ) D. J. Cardin and M. F. Lappert, Chem. Cornm., 1966, 506; ( c ) W. P. Neumann,
J. Pedain, and R. Sommer, Annalen, 1966, 694, 9.
260 K. Jones and M. F. Lappert, OrganometdZic Chem. Rev., 1966,1, 67.
261 (a) M. F. Shostakovskii, N. V. Komarov, I, S. Guseva, V. K. Misyunas, A. M.
Sklyanova, and T. D. Burnashova, DokZady Chem., 1966, 163, 678; ( b ) A. G. Davies,
T. N. Mitchell, and W. R. Symes, J . Chem. SOC.( C ) , 1966, 1311; (c) A. J. Bloodworth
and A. G. Davies, ibid., p. 299.
F. Bonati, S. Cenini, and R. Ugo, Rend. Prim0 Lembardo Sci. Lettere, 1965,
A , 99, 825.
E. W. Abel, D. B. Brady, and B. C. Crosse, J . Organometallic Chem., 1966, 5,
260; R. C. Poller and J. A. Spillman, ibid., 1966, 6, 668.
264 E. W. Abel, B. C. Crosse, and G. V. Hutson, Chem. and Ind., 1966, 238.
26s J. D. Cotton, J. Duckworth, S. A. R. Knox, P. F. Lindley, I. Paul, F. G. A.
Stone, and P. Woodward, Chem. Comrn., 1966, 253; F. Bonati, S. Cenini, D. Morelli,
and R. Ugo, J . Chem. SOC.( A ) , 1966, 1052.
2 6 6 (a) R. Ugo, F. Cariarti, F. Bonati, S. Cenini, and D. Morelli, Ricerca Sci., 1966,
86, 253; ( b ) G. W. Parshall, J . Amer. Chem. Soc., 1966, 88, 704.
2 6 7 ( a )A. Mohammed and D. P. N. Satchell, J . Chem. SOC. ( B ) , 1966, 527; ( b ) C. C.
Addison and W. B. Simpson, J . Chem. SOC.( A ) ,1966, 776.
s6* ( a ) J. P. Clark and C. J. Wilkins, J . Chem. SOC.( A ) , 1966, 871; ( b ) F. W . B.
Einstein and 33. R. Penfold,Chem. Comm., 1966,780.
2 6 9 C. E. Freidline and R. S. Tobias, Inorg. Chern., 1966, 6, 354.
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D O W N S , E B S W O R T H A N D T U R N E R : THE T Y P I C A L E L E M E N T S 167
NO,- in solution, in contrast to the behaviour of Me,Sn2+. The formation
and properties of PbCl, and its derivatives have been re~iewed.27~In
(Me3Pb),M (M = P, As) the infrared spectra imply that the molecules are
pyramidal a t M; the Sb derivatives could not be 0btained.~7l Triorganolead

borohydrides,272 made from R,PbOMe and B2H6, are liquid at -30°, and
decompose at room temperature to R6Pb2; with MeOH they give R3PbH a t
-78". Exchange between R,SnH and R,Pb-imidazole derivatives has
been used to generate P b hydrides for addition in situ to unsaturated
systems;273 addition of Pb-OR 274a and Pb-N 274b to multiple bonds has
been studied. The infrared spectra of R,Pb(SeCN) and Ph,Pb(SeCN),
indicate that the compounds do not contain Pb-N bonds.275
Nitrogen. A collection of reviews dealing with aspects of the inorganic
chemistry of N has been p~blished.~760Several systems involving the
reaction of nitrogen gas with transition-metal ions have been reported.276b
The configuration a t N in aniline 2770 and in dimethylaniline 277b is non-
planar; the n.m.r. spectrum of (C3F7)2NOC,F7, made from (C,E',),NO and
C3F71,indicates slow inversion at N.277c The red adduct 277d NH,I,NH, loses
NH3 under a vacuum a t -go", and at -70" it gives NHI,. A review of
inorganic nitrogen-iodine compounds has been p~blished.~77*
The salts (ClCH:NH2)+SbC1,- and (C12C:NH2)+SbC1,-react with water or
alcohols 278 to substitute OR or OH for C1 bound to carbon. Reaction
between MeSCl or CF,SCl and [(CF3)2N]2Hggives 27D0 (CF3),NSMe or
(CP,),NSCF, ; cyanogen chloride reacts with (CF,),NCl to produce 279b
(CF,),NN:CCl,, which forms [( CF,),NNCF,],Hg with HgF2, and (C3F8N2)2
with NaF. Irradiation of m,PF, gives several radicals,280among which
PF2and N2H,+ (formed from NH,+) were identified by e.s.r. Potassamide
and (Me,NNH,)+Cl- in liquid ammonia form Me,"€€, a hygroscopic,
explosive solid, most satisfactorily handled as its adduct with two molecules
of butanol, which gives Me,NNCN with CCI, and behaves as a strong base.281
The instability of the explosive N,H7SO4, produced from anhydrous N2H4
270 J. Szychlinski, Wi&o8ci Chem., 1966, 20,495.
271 H. Schuxnann, A. Roth, 0. Stelzer, and M. Schmidt, Inorg. Nuclear Chem. Letters,
1966, 2, 311.
2 7 2 E. Amberger and R. Honigschmid-Grossich,Chern. Ber., 1966, 99, 1673.
2 7 5 H. M. J. C. Creemers, A. J. Leusink, J. G. Noltes, and G. J. M. van der Kerk,
Tetrahedron Letters, 1966, 3167.
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( b ) W. P. Neurnann and K. Kiihlein, Tetrahedron Letters, 1966, 3415.
176 E. E. Aynsley, N. N. Greenwood, G. Hunter, and M. J. Sprague, J. Chem. SOC.
( A ) ,1966, 1344.
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Elsevier, vol. 1, 1966; (b) M. E. Vol'pin and V. B. Shur, Nature, 1966, 209, 1236; K. B.
Yatsimirskii and V. K. Pavlova, Doklady Chem., 1965, 165, 1088.
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Forsch., 1966, 5, 663.
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1823; (b) R. C. Dobbie and H. J. EmelBus, J . Chem. SOC.( A ) ,1966, 933.
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View Article Online
and H3N+*S03-,may imply that the compound is a derivative of triazine.28"

Salts of the substituted triazanium ion 282b H2NNR2*NH2+,are obtained
from H2NCl and either R,"H, or (CH,O),PNR,. The adducts RN,,SbCl,
react with R'C1 (R = Me or H; R = H or Me,C) at -78" to give

adducts 282c formulated as [RR'"N]+SbCl,-; the most thermally stable is
H,N,+SbCl,-, which loses N2in boiling CH2C12. The thermal decomposition
of M(N,), (M = Crt, Sr, Ba) in some organic solvents gives M&, a black
powder 283 which may contain N4s-.
The microwave spectrum of N203indicates a planar molecule with
non-equivalent N atoms (N-N = 1-85& 0.03A); the microwave spectrum
of trans-HNO, has been obtained 284b from a mixture of NO, NO,, and H20,
and the infrared spectra of both cis- and trans-forms in the vapour and solid
have been recorded.28k The hydrogen-bonded anions H(N02)2- and
H(N03),- have been obtained as salts of large cati0ns.~8~The infrared
spectrum of NO,AsF,, together with X-ray powder data, suggests that the
compound may be a mixture of salts of the NO+ and NO2+ions;286u Raman
spectroscopy 288b indicates that N,O, gives NO2+ in SeO,. Irradiation of
NOCl and C2F4 gives (among other products) (C1CF2CF,)2NON0,from
which the relatively stable radical (C1CF2CE",),N0 has been obtained.287
Fluorination of H2NS(0),NMe2at 30"gives (with a little MeNF,) Me,NF,
an unstable liquid giving an equimolar adduct with HC1 in which the N-I?
bond is apparently preserved.288a A simple way of preparing FNO from
N204and KF or CsF has been described.2s8b The new compound O", has
been obtained by different methods;289it is a strong oxidizing agent, and
gives 1 : 1 adducts with MF, (M = As or Sb) formulated as P2NO+MF6-.
Heating of NF3,F,, and SbF, under pressure gives Z9Oa NF,+SbF,-, and the
action of a glow dischargeon NF,,F,, and AsF, at -78" gives 29*b NF4+AsF6-.
The solids decompose at 270"(Ad?,-) orm. 300" (SbF,-); the As(v) derivative
is hygroscopic and readily hydrolysed, and its crystal structure resembles
that of PC14+PCl,-.
The chemistry of NF, has been re~iewed.2~1Properties of NF compounds
such as electron a m t i e s and ionisation potentials have been calculated
2 8 2 ( a ) F. Feh6r and K.-H. Linke,2. anorg. Chm., 1966, 344, 18; ( b ) K. Utvary and
H. H. Sisler, Inorg. Chem., 1966, 5, 1835; (c) A. Schmidt, Chem. Ber., 1966, 99, 2976.
28s Y. Okamoto and J. C. Goswami, Inorg. Chem., 1966, 5, 1281.
2 8 4 (a) R. L . Kuczkowski, J . Amer. Chem. SOC.,1965, 87, 5259; ( b ) A. P. Cox and
R. L. Kuczkowski, ibid., 1966, 88, 5071; ( c ) G. E. McGraw, D. L. Bernitt, and I. C.
Hisatsune, J . Chem. Phys., 1966, 45, 1392.
286 B. D. Faithful and D. 0.Tuck, Chem. and Ind., 1966, 992; B. D. Faithful,
R. D. Gillard, D. G. Tuck, and R. Ugo, J . Chem. SOC.( A ) ,1966, 1185.
2 8 6 (a) S. I. Morrow and A. R. Young, Inorg. Nuclear Chem. Letters, 1966, 2, 349;
(b) G. Kempe and D. Seifert, 2. anorg. Chem., 1966, 348, 124.
1966, 88, 480.
2 8 7 W. D. Blackley, J . A w r . Chem. SOC.,
(a)R. A. Wiesboeck and J. K. Ruff, Inorg. Chem., 1966,5,1629; ( b ) C . T. RrttclXe
and J. M. Shreeve, Chem. Comm., 1966, 674.
B89 N. Bartlett, J. Passmore, and F. J. Wells, Ghem. Comm., 1966, 213; W. B. Fox,
J. S. MacKenzie, N. Vanderkois, B. Sukornik, C. A. Warnser, J. R. Holmes, R. E.
Eibeck, and B. B. Stewart, J . Amer. Chem. SOC.,1966, 88, 2604.
890 (a)W. E. Tolberg, R . T. Rewick, R. S. Stringham, and M. E. Hill, Inorg. Nuclear
Chem. Lettera, 1966, 2, 79; (b) J. P. Guertin, K. 0. Christe, and A. E. Pavlath, Inorg.
Chem., 1966, 5, 1921.
2 9 1 C. B. Colburn, Chem. in Britain, 1966, 2, 336.
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D O W N S , E B S W O R T H A N D T U R N E R : T H E TYPICAL E L E M E N T S 169
using Huckel LCAO-MO meth0ds.2~~~ The acid-catalysed exchange between

HNE,and D,O has been investigated.292b There was no evidence of pro-
tonation of IE",by a variety of protonic acids;292c, d a, 1 : 1 complex is
apparently formed with AIMe, a t -78", which loses CH4a t that temperature,
but reaction with GaMe, to liberate CH, is slow a t room temperature.2920
Reactions of RNF, with organolithium reagents and with nitric acid have
been ~tudied,2~2~and the hydrolyses of NF,, N2F4,and both cis- and trans-
N,F2 investigated.292f Fluorination of buffered aqueous H2NCIN gives
N
zzc: II
N
Q-0 P
(26; Z = F)
(27; Z = RF)
F2CN2,identified spectroscopically 293a as F,NCN rather than FNCNF; with

CsF it gives (26). The action of Pb(OAc), on (RF)2C=N*NH2
gives (R,),CNN and reaction between the same oxidizing agent and
I I
(CF,),C-NE-NH gives perfluorodimethyldiazirine 2936 (27). Mixtures of
CO and N2F4 afford F,NCFO when irradiated.2ga Perfiuorohydrazinereacts
with CFBr, and related compounds 293d to form FN: CFBr. Adducts of SbF,
(Sb :N = 1 : 1) with N2F4 and with both cis- and trans-N,F, have been
obtained ;294 the N2Fzadducts give exclusively cis-N2F, on decomposition.
Spectroscopic evidence leads to the formulation of N2F,,2SbF5 as
FzN"+Sb2Fll- and of N2F,,2SbF, as N2F+Sb2F11-. Fluorination of NaN,
can be controlled 295 t o give either trans or cis,trans mixtures of N2F2. The
cation Me,C=N(Me)F+ is formed296 when ButNF, reacts with BF, or
H2S04; the fluorination of cyanuric chloride 297u or of 297b H2NC(:NH) S02H
gives CF2(NF2),.
Phosphorus. The structure of violet P is based on Ps groups (atoms as in
As,S,) and P, groups, linked through further P atoms to give an infinite tube-
like s t r u c t ~ r e .Irradiation
~~~~ of PH, in a Kr matrix at 4°K gives 298b PH,,
but irradiation of ASH, gives only As and H atoms. Reactions involving
292 ( a ) J. J. Kaufman, I;. A. Burnelle, and J. R. Hamann, Adv. Chem. Ser., 1966,
54,s; ( b )W. E. Becker and F. J. Impastato, ibid., p. 132; (c) J. N. Keith, R. J. Douthart,
W. K. Sumida, and I. J. Solomon, ibid., p. 141; ( d ) A. D. Craig, G . A. Ward, C. M.
Wright, and J. C. W. Chien, ibid., p. 148; (e) H. F. Smith, J. A. Castellano, and D. D.
Perry, ibid., p. 155; (f)G. L. Hurst and S. I. Khayat, ibid., p. 245.
293 (a)M. D. Meyers and S. Frank, Inorg. Chem., 1966, 5, 1455; (b) D. M. Gale,
W. J. Middleton and C. G. Krespan, J. Amer. Chem. SOC.,1966, 88, 3617; (c) G. W.
Fraser and J. M. Shreeve, Inwg. Chem., 1965, 4, 1497; (d) D. H. Dybrig, ibid., 1966,
5, 1795.
a 9 4 J. K. Ruff, Imrg. Chem., 1966, 5, 1791.
2 Q b H. W. Roesky, 0. Glemser, and D. Bormann, Chm. Ber., 1966, 99, 1589.
2 9 6 K. Baum and H. M. Nelson, J. A m r . Chem. Soc., 1966, 88,4459.
8 * 7 (a)M. A. Englin, S. P. Makaror, S. S. Dubov and A. Y a . Yakubovich, J . Gem.
Chem. (U.X.S.R.), 1965,3!5,1419; ( b ) R. J. Koshar, D. R. Husted, and R. A. Meiklejohn,
J . Org. Chem., 1966, 31,4232.
2 9 8 (a)H. Thurn and H. Krebs, Angew. C h . ,Internat. Edn., 1966,5,1047; (b) R. L.
Morehouse, J. J. Christiansen, and W. Gordy, J. Chem. Phys., 1966, 45, 1747.
View Article Online
170 I N O R Q A N I C CHEMISTRY
apecies in which an unpaired electron is associated with a P atom have been

reviewed.20Qa Alkali metals react with phenylbiphenylenephosphine in
THF ,Oob (28), as with triphenylphosphine,2Q9cto remove the phenyl group.
The anion formed reacts with more alkali metal, giving a radical-anion which
dimerizes through P. The importance of (Ipd)minteractions, and of con-
jugation through P, has been discussed in relation fo the U.V. spectra of
phenylphosphorane~,~OO~ of phosphine ylides,sooband of other species.3m
The structural chemistry of phosphorus compounds has been extensively
reviewed.801o I n the crystal, the angle 301b at or-C in Ph3P=c----C=0 is
14!55". The n.m.r. spectra of (p-tolyl),M (M = P, As, Sb) show a single Me-
proton resonance, indicating rapid positional exchange ; in spirophos-
phoranes (29), two Me-proton resonances are observed when R is 1-naphthyl
or 9-anthryl, implying that the bulky substituents slow the exchange.Wza
The bond angles a t P in PF, and related species have been discussed in
terms of electron-pair repulsions and delocalised molecular orbital
theory.302: The n.m.r. spectra of MH3, MH2- (M = P, As),MeAsH,, and
MeAsH- have been determined, and the relative acidities of the hydrides
estimated. 230
The mass spectra of the products of thermaI decomposition of P2H4 or the
hydrolysis of Ca3P2have led to the postulation 303 of a number of ring and
chain derivatives, from P2H2and P3H5to PI2H4and PI4H. Hydrolysis of
M3N2 mixed with M3Z2 (M = Mg, Ca; 2 = P, As) gives Z3H5,Z2NH4, and
Me Me
S
R- - PtBun3
s-
Me Me
I n DMF, KPH, and P4 com-

related species, identified by mass ~pectra.~04
bine to give KP,H2, formulated 305 as containing P,H,-. Methanolysis of
(CF3P),gives H(CF,P),H, and the less stable H(CF3P),H is probably formed
from (CF3P),and n-dodecyl alcoho1;306 the reaction of MeP(NMe,), with
8 9 0 ( a ) C . Walling and M. S. Pearson, " Topics in Phosphorus Chemistry," 1966, 3,
1; (b) A. D. Britt and E. T. Kaiser, J . Org. Chem., 1966,31,112; (c)A. D. Britt and E. T.
Kaiser, J . Phys. Chem., 1966, 69, 2775.
i+oo ( a )J. E. Bissey and H. Goldwhite, Tetrahedron Letters, 1966, 3247; ( b ) H. Fischer
and H. Fischer, Chem. Ber., 1966, 99, 658; (c) H. Goetz and H. Juds, Annden, 1966,
098, 1.
*01 (a)D. E. C. Corbridge, " Topics in Phosphorus Chemistry," 1966, 3, 57; ( b ) J. J.
Daly and P. J. Wheatley, J . Chem. SOC.( A ) ,1966, 1703.
( a ) D. Hellwinkel, Angew. Chem., Internat. Edn., 1966, 5, 726; ( b ) R. J. Cillespie,
I w g . Chem., 1966, 5, 1634; (c) L. S. Bartell, Inorg. Chem., 1966, 6, 1635.
SO8 M. Baudler, H. Stiindeke, M. Borgardt, and H. Strabel, Naturwiss., 1965, 52,
345; M. Baudler, H. Stiindeke, M. Borgardt, H. Strabel, and J. Dobbers, ibid., 1966,
63, 106; T. P. Fehlner, J . Amer. Chem. SOC.,1966,88, 1819, 2163.
P. Royen and C. RocktBschel, 2.anorg. Chem., 1966, 346, 290.
SO5 F. Knoll and G. Bergerhoff, Monatsh., 1966, 97, 808.
808 A. B. Burg and L. K. Peterson,Inorg. Chem., 1966, 5, 943.
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D O W N S , E B S W O R T H A N D T U R N E R : THE T Y P I C A L E L E M E N T S 171
HPPh, gives 307a MeP(PPh,),, which reacts with S, forming MeP(PSPh,),;

it is concluded from the n.m.r. spectrum of (PhMe)PP(MePh)with (2,4,6)-
trideuterio-phenyl groups that inversion is slow a t room temperature 307*
but fast at 180".

The molecular complexity of (PhP), in solution is confusing, perhaps
because the system is more labile than was once believed. I n the solid, there
are pentameric (m.p. 149--50"), hexameric, and more complex modifica-
ti0115.3070 The form of m.p. 149-50" has a mol. wt. in solution corres-
ponding initially to (PPh),, but the value drops with time in HCBr, or even
on standing as solid a t -18". The 31P n.m.r. spectra of melts of (PhP),
contain peaks assigned to monomeric PhP, as well as to cyclic forms.308b
The action of alkali metals M on (PhP), m.p. 154-156" dissolved in THF or
dioxan gives MJPhP),, sometimes solvated (n = 4,3,2,depending on M and
conditions), formulated with linear P-P systems; with water, they give H,
and (PhP), if n = 4,the linear H(PPh),H being a presumed intermediate, but
if n = 2 or 3 hydrolysis involves P-P fissi0n.~08~ Under reflux, (PhP), (m.p.
154-156") reacts with K in THE' to give red K,(PPh),, assigned a cyclic
structure because the 31Pn.m.r. spectrum indicates equivalent P atoms.308d
The mass spectra of mixtures of (MeP), and (EtP), that had previously been
distilled at 150" showed species 3 0 Et,Me,-,P,
~ (n = 0-5); the mass spec-
trum of (EtP), contained s~~~peaks due to (EtP),. The action of Hg on
C,F,PX, (X = Br, I)gives 310 (C,F,P),, with n = 5 (mass spectra, mol. wt.
in CH,Br,). The action 311 of S on (CF3P),gives (CF,P),S, which reacts with
Me,P to give Me3PS.
The compoundsPHF, and PH,F3 have been obtained from H,,P(O)(OH),-,
(n = 1 or 2) in anhydrous HF; they are monomers as vapours, though there
is evidence that PH,F, is associated (b.p. 3.8"). The n.m.r. spectra indicate
time-dependent exchange processes, but the infrared spectra are consistent
~ ~ " action of HI on
with equatorial H atoms in trigonal b i p y r a m i d ~ . ~The
Me2NPSF, gives 312b SPF,H. The heat of formation of PF, by fluorine
bomb calorimetry is 313 dHf(298) (a-white P) PI?, = -380.3 & 0.3 kcal./
mole. The action 314a of CuCN or Cu20 on PF,I (made 315 from F,PNMe,
and HI) gives F2PCN or P,POPF,; the action314a, of Hg on PF21forms
PP,, which gives a weak e.s.r. signal,314uperhaps due to PF,. The vibra-
tional spectra of P,I, in CS, indicate that the molecule has the trans
(a) L. Maier, Helv. Chim. Acta, 1966, 49, 1119; ( b ) J. D. Lambert and D. C.
Mueller, J . Amer. Chem. Soc., 1966, 88, 3669.
( a ) M. Baudler, K. Kipker, and H.-W. Valpertz, Natuwiss., 1966, 53, 612;
( b ) E. Fluck and K. Issleib, 2. Naturforsch., 1966,21b, 736; ( c ) K. Issleib and K. Krech,
Chem. Ber., 1966, 99, 1310; ( d ) K. Issleib and E. Fluck, Angew. Chem., Internat. Edn.,
1966, 5, 687.
( a ) K. Schmidt, R. Schroer, and H. Achenbach, Angew. Chem., Internat. Edn.,
1966,5, 316; ( b ) A. H. Cowley and R. P. Pinnell, Inorg. Chem., 1966, 5, 1469.
A. H. Cowley and R. P. Pinnell, J . Amer. Chern. SOC.,1966, 88, 4533.
sll A. B. Burg, J . Amer. Chem. Soc., 1966, 88,4298.
s l a (a)R. R. Holmes and R. N. Storey, Inorg. Chem., 1966,5,2146; (b) T. L. Charlton
and R. G. Cavell, Chem. C m m . , 1966, 763.
s l s P. A. G. O'Hare and W. N. Hubbard, Trans. Farday Soc., 1966, 62,2709.
s14 ( a ) R. W. Rudolph, R. C. Taylor, and R. W. Parry, J. Amer. Chem. Soc., 1966,
88, 3729; ( 6 ) M. Lustig, J. K. Ruff, and C. B. Colburn, J . Amer. Chem. SOC.,1966, 88,
3876.
R. W. Rudolph, J. G . Mom, and R. W. Parry, Inorg. Chem., 1966,5, 1464.
View Article Online
configuration in solvents, as in the contrary to an earlier report ;some

details of the vibrational and the n.m.r. spectra are consistent with the
equilibrium 3P214= QP, 4P1,. +
Several phosphane oxides (from P,H,O to P,H50),the products of hydro-

lysis of Ca,P2, have been identified from their mass spectra.s17 A number of
reactions of P,O, have been investigated;S1g"it behaves as a quadridentate,
non-chelating ligand.31gb The formulae of various polyphosphites have been
deduced S18c from the conductivitiesof solutions of phosphites of Rb and Cs in
aqueous &PO,. The reaction of SO, with MsP3OlO(M = Na, K) gives P,05
and S2072- (Na) or S,O,,Z-(K); heating of the products of the reaction with
the Na salt to their m.p. gave SO,, leaving sulphate-phosphate glasses.SIQO
Thermodynamic properties associated with ionisation of H3PO4, H4P20,,
and H,P301, have been determined,319band the acidity functions of
(X,Y)P(O)OHin DMSO and ethylene glycol (X, Y may be PhO, cyclohexyl,
H,OH, Ph, cyclohexyloxy) have been determined using primary aniline indi-
cator~.~l~ c reaction between POBr, and FS0200S02F follows the
The
equation 820a
POBr, + GFO,SOOSO,F = OP(OSO,F), + 3Br(OS02F),
Phosphates have been shown cryoscopically and by conductivity to give
P(OH),f in H,SO,; Ph,P and (EtO),P are fully protonated, although
POP, and POCl, behave as non-electrolytes.320b Sodium triphosphate and
fluoride ion react in water a t 80" to give 320c (P,O,F)-, which degrades
slowly, forming FP0,-, FP,063-, and P,074-.The action of SPC1,
on aqueous ammonia gives NH,+[POS(NH,),]-, which hydrolyses to
(NH,),[PO,S(NH,)] in the presence of acid; 3,1 in 20% HF, the two anions
give [POSF,]- and [PO,SF]2-, of which the former hydrolyses to the latter
in HF-free aqueous acid. Passage of an electrodeless glow discharge through
a, mixture of PH, and RSH (R = H or Me) gives (amongother products)
H,PSR (identified by mass spectra).322u In benzene, (RPS,), reacts
with Bun3P,giving crystals formulated as (30);322b the action of NaHX (X =
316 ( a ) S . G. Frankiss, F. A. Miller, H. Stammreich, and Th. Teizeira Sans, Chem.

Comm., 1966, 318; ( b ) R. L . Carroll and A. H. Cowley, ibid., p. 872.
317 M. Baudler, H. Stfindeke, J. Dobbers, M. Borgardt, and H. Strabel, Natzlwiss.,
1966, 53, 251.
318 ( a ) J. G . Riess and J. R. van Wazer, Inorg. Chem., 1966, 5, 178; (b) J. G. Riess
and J. R. van Wazer, J . Amer. Chem. SOC.,1966, 88, 2166; (c) M. Ebert and J. Cipere,
CoEl. Czech. Chem. Comm., 1966, 31, 1.
319 ( a ) S. N. Kondrat'ev and S. I. Mel'nikova, R w s . J . Inorg. Chem., 1966, 11, 429;
( b ) R. R. Irani and T. Taulli, J . Inorg. Nuclear Chem., 1966, 28, 1011; ( c ) A. G . Cook
and G. W. Mason, ibid., p. 2579.
320 (a) D. D. Des Marteau and G. H. Cady, Irwrg. Chem., 1966, 5, 1829; ( b ) R. J.
Gillespie, R. Kepoor and E. A. Robinson, Canad. J. Chem., 1966, 44, 1203; (c) R. E.
Mesmer, J . Inorg. Nuclear Chem., 1966, 28, 691.
831 H. H. Falius, Angew. Chm., Internat. Edn., 1966, 5, 266.
323 ( a ) P. W. Shenk and B. Leutner, Angew. Chem., Internat. Edn., 1966, 5, 898;
( b ) E. Fluck and H. Binder, ibid., p. 666.
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D O W N S , E B S W O R T H A N D T U R N E R : T H E T Y P I C A L E L E M E N T S 173
S or Se) on Et,PSeCl gives salts 323a of (Et,PSeX),-; the species RRR"P

react with KNCSe t o give RRR"PSe, and R,P(Se)H has been syn-
thesised from R,PH and red ~elenium.3~% The compound (Et,PSSe), is
linked through Se and not through S in the

The reactions of organic P(m)-N compounds have been r e v i e ~ e d . ~ ~ d
The very acidic (Ph,PS),NH is formed 325u from Ph,P(S)NFI, and
Ph,P(S)Cl ; methylation gives (Ph,PSMe),N+X-. The dimer (PhNPCl,),
reacts with liquid ammonia, producing a solid formulated 325b as
[PhNHP(NH,),NP(NH,),NHPh] +C1-. The species obtained by the thermal
decomposition of (R,N) (RNH)P(Z)NHR (Z = 0 or S),previously formulated
as monomers?give molecular weights in solution that correspond to dimers."a
The reaction of (CF,),NCI with PF, or PF2C1gives 3 2 7 a (CF3),NPF,C1 or
(CF,),NPF,Cl, ; with (CF,),NCl and M(CF,),, the perfluoro-derivatives
[(CF,),N],M(CP,),-, (n = 1,2, M = P, As; rt = 3, M = P) are formed.
The reaction with Sb(CF,), is more c0mplex.~~7~ Dimeric (PhCC1: N),
reacts 328 with R,P- to give [Ph(R,P)C:N],, and with RP2- to give (31).
The chemistry of phosphonitrilic compounds has been revie~ed.3,~In
(PNCl),, the variations in ionisation potential and in donor properties with
n are interpreted in terms of modulation of the main, out-of-plane n-inter-
actions with in-plane n' Huckel-type interactions;330athe effects of side-
group repulsion on the relative thermal stabilities of PN polymers has been
discussed.330b In the crystal, (MeNPCI,), contains a planar 4-membered
PN ring, the P atoms at the centres of trigonal bipyramids;331athe species
(RNPC13)2react 331b with SO,, giving (RNPOCl),, in which C1 may be
replaced by Z ( = SR, NR,) uisng Me,SiZ. Sulphamide and PCl, react
,N=P$lz EtOzC, ,S, ,COzEt
02s\ NM e ,c=c\ /c=c,
N=PCI, EtOzC S COlEt
(3 2) (33) (34)
[Reproduced from 1%.F. Hawthorne and R. L. Pilling,
J . Amer. Chem. SOC.,1966, 88, 3873.1
together to form C1,P: N*SO,*N:PCI,, which with ammonia gives the ring-
anion (32), and with (Me,Si),NMe the neutral compound (33).331c Many
derivatives of (PN), rings have been prepared, with substituents such as
a2s ( a )W. Kuchen and B. Knop, Chem. Ber., 1966,99,1663; ( b )P. Nicpon and D. W.
Meek, Inorg. Chm., 1966, 5, 1297; ( c ) L.Maier, HeZv. Chim. Acta, 1966, 49, 1000; ( d ) S.
Husebye, Acta Chem. Scand., 1966, 20, 51.
s 2 4 R. Burgada, Ann. Chim. (France), 1966, 14, 15.
s26 ( a ) A. Schmidpeter and H. Groeger, 2. anorg. Chem., 1966, 345, 106; ( b ) K.
Utvary, V. Gutmann, and Ch. Kemenater, Monatsh., 1965, 96, 1751.
326 H. Bock and W. Wiegriiber, Chem. Ber., 1966, 99, 377.
s 2 7 ( a ) H. J. Emelkus and T. Onak, J . Chem. SOC.( A ) , 1966, 1291; ( 6 ) H.-G. Ang
and H. J. EmelBus, Chem. Comm., 1966, 460.
3a8 K. Issleib and A. Balszuweit, Chm. Ber., 1966, 99, 1316.
82s T. Yvornault and G. Casteignau, Bull. SOC. chim. France, 1966, 1469.
( a ) C . E. Brion, D. J. Oldfield, and N. L. Paddock, Chem. Comm., 1966, 226;
( b ) H. R . Allcock, Inorg. Chem., 1966, 5 , 1320.
831 (a)L. G. Hoard and R. A. Jacobson, J . C h m . Soc. ( A ) ,1966, 1203; ( b ) M. Green,
R. N. Haszeldine, and G. S. A. Hopkins, &id., p. 1766; ( c ) M. Becke-Goehring,K. Bayer,
and T . M a m , 2. anorg. Chem., 1966, 348, 143.
View Article Online
174 INORGANIU UHEMISTRY
ArNH 382a or RS,332band aromatic vic-dihydroxy-, or diamino-compounds,

or dithiols, which give cyclised pr0ducts.33~~Isomers have been identified,
usually by n.m.r., in mixed Ph-PhO, Ph-NMe,, and Ph-NHMe derivative~,~3~O
in mixed Me2N-OPh in mixed Me,N-NHPri species,s3&and in

mixed Cl-NC5H1033Sd and Cl-KKR compounds.~3~The formation and
basicities of some of these isomers has led to generalisations about the elec-
tronic structures and substitution reactions of the systems,38a,C, d , 6 and a,
" cis '' effect has been proposed.333d The compound (N,P,Ph,OH) is a very
weak acid, perhaps because the anion is only slightly stabilized by

r e s ~ n a n c e . ~Of
~ ~the
f four geometric isomers of (PNPhCl),, three have been
identified 334a by n.m.r. ; the ring in (NPCI,)5 is very nearly planar.334b Pyri-
dine reacts with (PNCl,), to form an unstable solid 334e P3N&l6py6, which
with water gives what may be (PNpyOH),, and ultimately [PN(OH),],.
The chemistry of P-containing heterocyclic C O ~ ~ O U and ~ ~ofS deriva-
, ~ ~ ~ ~
tives s358 of Ph,P and Ph5As, has been reviewed; the compounds Ph,PCl
and Ph,PC:PPh, give 336a [(Ph,P),C*PPh,]+Cl- which reacts with excess of
Me1 to form [(Ph,P),C*PPh,MeJ2+21-. The compound described as
(Me,N),PCF, has been re-identified 336b as (Me2N)3PF2. Ketones of the
general form RCOPR', have been prepared,,,& and their reactions studied ;
they are colourless when R is alkyl, but coloured when R is aryl. The direct
reaction under vigorous conditions between P, and MeCl or MeBr has been
used to make Me,PCl and Me4PBr in high yields.336d A number of new
(C,F,)P-derivatives has been prepared.337
Unlike Ph,N, Ph3M (M = P, As, Sb) forms 1 : 1adducts 338a with C6Me6;
the compounds of composition Ph,PX (X = Br, I) are apparently 338b
Ph,PHX, which react with I, to give Ph,PI, and HI. In MeCN, the species
Ph3MX2 (X = C1, Br, I) behave as strong electrolytes (M = P), weak
electrolytes (M = As), or non-electrolytes (M = Sb, Bi); for the systems
Ph,PX, and X, in MeCN (X = Br or I), conductometric titration indicates
that Ph3PX+ and X 3 - are formed.,,& The charge-transfer complexes 3s88
Ph3M,12(M = N, P, As, Sb) change with time to Ph,MI+I- when M = P, As.
*S3 ( a ) H. LederIe, G. Ottman and E. Kober, Inorg. Chem., 1966, 5, 1818; ( b ) A. P.
Carroll and R. A. Shaw, J . Chem. SOC.( A ) ,1966,914; ( c ) H. R. Allcock and R. L. Kugel,
Inorg. Chem., 1966, 5, 1016.
338 ( a ) C. T. Ford, J. M. Barr, F. E. Dickson, and I. I. Bezman, Inorg. Chm., 1966,
5, 351; ( b ) D. Bell, B. W. Fitzsimmons, R. Keat, and R. A. Shaw,J . Chem. SOC.( A ) ,
1966, 1680; (c) S. K. Das, R. Keat, R. A. Shaw, and B. C. Smith, ibid., p. 1677; ( d ) R.
Keat and R. A. Shaw, ibid., p. 908; (e)D. Feakins, W. A. Lart, S. N. Nabi, and R. A.
Shaw, ibid., p. 1831 ; (f)C. D. Schmulbach and V. R. Miller, Inorg. Chem., 1966,5,1621.
884 ( a ) B. Gmshkin, A. J. Berlin, J. L. McClanahan, and R. 0. Rice, Inorg. Chem.,
1966, 5, 172; ( b ) A. W. Schleuter and R. A. Jacobson, J . Amer. Chem. SOC.,1966, 88,
2051; ( c ) B. I. Stepanov and G. I. Migachev, J . Qen. Chem. fU.S.S.R.), 1965, 35, 2245;
( d ) H. R. Allcock, R. L. Kugel, and K. J. Valany, Inorg. Chem., 1966, 5, 1709.
3 8 5 ( a ) G. Miirkl, Angew. Chem., Internat. Edn., 1965, 4, 1023; ( b ) G. Wittig, Bull.
SOC.chim. France, 1966, 1162.
8 * 6 (a) G. H. Binun and C. N. Matthewa, J . Arne?-.Chem. SOC., 1966, 88,4198; ( b ) F.
Ramirez and C. P. Smith, Tetrahedron Letters, 1966, 3651; ( c ) K. Issleib and 0. LOW,
2. anorg. Chem., 1966, 346, 241; ( d ) L. Maier, Helv. Chim. Acta, 1966, 49, 2458.
5 3 7 H. J. Emelhus and J. M. Miller, J . Inorg. Nuclear Chm., 1966, 28, 662; 15. Fild,
0. Glemser, and I. Hollenberg, Naturwiss., 1966, 53, 130; M. Fild, 0. Glemser, and I.
Hollenberg, 2. Naturforsch., 1966, 21b, 920.
a** ( a )R. A. Shaw, B. C. Smith, and C. P. Thakur, Chem. Comm., 1966,228; ( b ) A. D.
Bevoridge, G. S. Harris, and D. S. Payne, J . Chem.SOC.( A ) ,1966,726; ( c )A. D. Beveridge
G. S. Harris, and F. Inglis, ibid., p. 520; ( d )K. R. Bharhr, S. N. Bhat, S. Singh, and
View Article Online
D O W N S , E B S W O R T H A N D T U R N E R : T H E TYPICAL E L E M E N T S 175
Solids formulated on the basis of their spectroscopic properties and their
conductivities in acetone as (Ph,PPX,O)+X- (X = C1, Br) are formed 338e
from Ph,P and OPX,.
The addition compounds of the pentahalides of Group V have been

revie~ed.33~aAdducts of MeCN, SO,, and Me,N with ME", (M = P, As, or
Sb) and B35,2sbF, are described; all the MeCN and Me,N adducta except
&F5, NMe, give conducting solutions 339b in MeCN. The adduct Me,O,PF,
decomposes 34Oa slowly a t room temperature to Me,0+PF6- and OPF,, but
Me,S,PF, gives PI?,, Me,S+PF,-, and (Me,SSMe)+PF6-. On the basis of
S, Se) stability is in the order 0 S > Se. -

v.p. and related measurements, it is concluded 3406 that in PF,, ZMe, (Z = 0,
Arsenic. I n As vapour 341 the tetrahedral As4 has d(As-As) 2.435 A.

There is evidence 342 from irreversible voltammigrams of millimolar &(m)
and As(v) that As(rv) is formed in ~*OM-HCIO,. I n crystalline MeAs(CN),,
as in As(CN),, the (AsCN)systems are apparently not linear.343QA method
for the preparation of pure As214is described;34sbthe compound is thermally
stable a t 150°, and some of its physical and chemical properties have been
determined.34" The chemistry of organoarsenic compounds has been
reviewed.344 The reaction between Ph,AsH and Et,M (M = Mg or Zn)
gives 345Q (Ph,As),M or (PhAsH),Zn ; several substituted aminoarsoniurn
chlorides and cyclic As-N systems have been prepared by treating Ph&s
or PhAsCl, with chloramine or mixtures of chloramine and ammonia ;345b
amines react with As(OMe),, forming 345c As-N ring systems with Me0 groups
bound to As; the action of As(NMe,), on aldehydes or ketones leads t o the
formation 345a of RRC(NMe,),. Non-volatile solid oxyfluorides ASOB',,
SbOF,, and SbO,F have been prepared 346a by the thermal decomposition of
the fluoride nitrates, themselves made from the fluoride chlorides and ClNO,.
A compound MeOAsF4,formulated as [AsF,(OMe),J +AsF6-,is produced 346b
by the action of MeOK on &F5 in c&?~',c1,; it gives a conducting solution in
AsF,. The preparation of (CF,),As*NR*P(CF,), [R = H, Me, P(CF,),]
from (CF,),AsCl and (CF3),PNHR in the presence of Me3N (R = H, Me) or
from [(CF,),P],NNa and (CF,),AsCl [R = P(CF,),J has been described;346c
the As-N bonds are broken readily by HCl, though less so by BCl, and BF,,
and it is deduced that (p4d)minteractions are weaker than are ( p 3 d ) n -
C. N. R. Rao, J . Inorg. Nuclear Chem., 1966, 28, 1915; ( e ) E. Lindner and H. Schless,
Chem. Ber., 1966, 99, 3331.
839 ( a )M. Webster, Chem. Rev., 1966, 66, 87; ( b ) I;. Kolditz and W. Rehak, 2.anorg.
Chem., 1966, 342, 32.
3 4 0 (a)R. A. Goodrich and P. M. Treichel, J . Amer. Chem. SOC.,1966, 88, 3509;
( b ) I. K. G.regor, Austral. J. Chem., 1966, 19, 1977.
8 4 1 Y.Morino, T. Ukaji, and T. Ito, Bull. Chem. SOC. Japan, 1966, 39, 64.
343 H. A. Catherino, J . Phys. Chem., 1966, 70, 1378.
343 ( a )E. 0 . Schlemperer and D. Britton, Aeta Cry&., 1966, 20, 777; ( b ) M. Baudler
and H.-J. Stassen, 2.anorg. Chem., 1966, 343, 244; (c) M. Baudler and H.-J. Stassen,
&id., 1966, 345, 182.
3 4 4 W. R. Cullen, Adv. Organometallic Chem., 1966, 4, 145.
84s ( a ) A. Tzschach and H. Hiickert, 2. Chem., 1966, 6, 265; ( b ) D. Ham, 2. anorg.
Chem., 1966, 347, 123; ( c ) H.Weingarten and W. A. White, J. Org. Chem., 1966, 31,
4041; ( d ) H.Weingarten end N. A. White, J. Org. Chem., 1966, 31, 4041.
348 (a)L. Kolditz and E. Rosel, 2. anorg. Chem., 1965, 341, 88; (a) L. Kolditz and
E. Rosel, I;. anorg. Chczm., 1965, 341, 88; (c) J. Singh and A. B. Burg, J . Amer. Chem.
SOC.,1966, 88, 718.
View Article Online
176 INOBGANIO CHEMISTRY
interactions. The action of Hg on CF3AsI, gives 347a (CF,As),, and possibly

(CF,As), ; CF3COC1 reacts with Me4As2, forming ,478 Me,AsCOCF, and
Me,AsCl. The arrangement of the four 0 atoms round As in the crystal of
K[As(C,H402),] could be regarded as based on a trigonal bipyramid, with a

stereochemically active lone-pair.348
Antimony. The crystal structures of the salts M,SbX, (M is Rb+,
Cs+, or NH4+; X is C1 or Br), which formally contain Sb(rv), show the
presence of Sb(m) and Sb(v); the Sb(v)Br,-octahedra are distorted, but
the Sb(m)Br,-octahedra are The stereochemistry 35* of Sb(v) has
been reviewed; solid SbC14Fis tetrameric, with octahedral Sb and F bridges
( LSbFSb = 173"), the Sb-F ring being slightly p u ~ k e r e d . S ~The ~~
vibrational spectra of Me,Sb have been assigned S 5 l b on the basis of a trigonal
bipyramid round Sb. The n.m.r. spectra of solutions of pairs of the
compounds Me3SbX2(X = I?, C1, Br,I) in CHCI, show 3 5 2 ~the presence of
mixed species a t -32"; exchange becomes rapid on the n.m.r. timescale a t
temperatures between 7O0(Br/I) and 150°(F/C1). The infrared spectra of
crystalline Me,SbX, (X, = F-, NO,-, CO,2-, SO4,-, Cr042-, C2042-)
indicate 352b that these compounds are molecular in the solid; attempts to
prepare Me,Sb2+(BF4),- or Me,Sb2f(SbE',)2- gave impure products and
Me,SbF,. The lH and 19Fn.m.r. spectra and the conductivities of solutions
of SbF, in HF are interpreted in terms of the formation of species H,F+ and
(SbnF5n+l)-; the abnormally high mobility of the H,F+ ion indicates a
Ins HF, SbP40S0,F solvolyses 353 to give
proton transfer m e ~ h a n i s m . ~ ~
SbF,- and HS0,F. The thermodynamics associated with solvation equi-
libria between SbCI, and a number of donor solvents have been investigated
spectrophotometrically and calorimetrically.354 Azo-compounds such as
PhNNPh form complexes with SbCl,, SbCl,, and BiCI,.
Bismuth. There is spectrophotometric evidence 356 to suggest the for-
mation of Bi+, Bi,3+ and a further associated species in solutions of Bi and
BiCl, in melts of NaCI/AlCI, or KCl/ZnCl,. The crystal structure of
Bi(H20),(N03)3 has been determined.357a The vibrational spectra of hydro-
lysed Bi(rn) perchlorate indicate that there is no change in the structure of the
cation on going from the solid to solution, and the frequencies have been
interpreted S67bin terms of the octahedral cage complex cation, Big(OH2)B6+.
Formation constants for the mixed complexes [Bi(SCN),Br]S- and
8 4 7 (a)A. H. Cowley, A. €3. Burg, and W. R. Cullen, J . Amer. Chem. SOC.,1966, 88,
3118; ( b ) W. R. Cullen and G . E. Styan, Canad. J. Chm., 1966, 44, 1225.
3 4 8 A . C. Skapski, Chem. Comm., 1966, 10.
349 S. A. Lawton and R. A. Jacobson, Inorg. Chem., 1966, 5, 743.
8 5 0 G. 0. Doak and G . 0.Long, Trans. New York Acad. Sci., 1966, 28, 402.
3 5 1 ( a ) EL Priess, 2. Chem., 1966, 6, 350; (b) A. J. Downs, R. Schmutzler, and I. A.
Steer, Chem. C o r n . , 1966, 221.
3 5 2 ( a ) G. G. Long, C. G. Moreland, G. 0. Doak, and M. Miller, Inorg. Chem., 1966,
5, 1358; (b) H. C. Clark and R.G . Goel, ibid., p. 998.
8 5 3 R. J. Gillespie asld K. C. MOSS,J . Chem. SOC.( A ) ,1966, 1170.
3 5 4 V. Gutmann, A. Steininger, and E. Wychera, Monatsh., 1966, 97,460.
8 5 5 L. A. Kazitsyna, N. B. Kupletskaya, V. A. Ptitsyna, M. N. Bochkareva, and
0.A. Rentov, Rztss. J . Org. Chem., 1966, 2, 567,570.
3 5 6 N. J. Bierrum, C. R. Boston, G . P. Smith, and H. L. Davis, Inorg. NucZear C h .
Letters, 1965, i, 141.-
3 5 7 ( a ) P. Herpin and K. Sudarsanen, Bull. SOC.France, MineraE Grist., 1965, 88,
690; ( b ) V. A. Maroni and T. G . Spiro, J . Amer. Chem. SOC.,1966, 88, 1410.
View Article Online
D O W N S , EBSWORTH A N D TURNER: THE TYPICAL ELEMENTS 177
[Bi(SCN),Br3l3-have been determined.358 The action of AgClO, on Ph,BiCl,
a t room temperature leads 859a to the formation of Ph4Bi+C10,-; treatment
of Ph,BiBr with pyridine gives 359b Ph,Bi and PhBiBr2,2py.
Group VI.-Oxygelz. The magnetic susceptibility of 02+ has been deter-

mined 360 from measurements with o,+PtF6- and NO+PfP6-. Oxygen
isotope exchange reactions of organic compounds have been reviewed.s61
The reactions of Lewis acids with MeO- in MeOH have been investigated
conductometrically, and several new derivatives have been prepared.36a
The chemistry of dissociated water vapour and related systems has been
a study of the products of an electrodeless discharge on mix-
tures of H atoms and H,O, vapour a t low pressures does not support the
suggestion that metastable intermediates (e.g., H204) are formed.36sb The
thermal stability of inorganic peroxy-compounds has been considered, 364a
and the chemistry of organometallic and organometalloid peroxides re-
viewed.s64b The photolysis of C,F20, gives CF(0)O radicals, thus con-
fbming 364c the suggested structure of the parent compound, FC(O)*O,-C(0)F;
this, when photolysed with SO,, gives FC(0)OSOaF. The material for-
mulated 365a as But,O,, formed by the action of Ph3PC1, on a mixture of
Ph,PO and ButOOH a t -78", has been described 3+35b from its physical
properties as Me,C( OOBut),.
An improved preparation of 04F2,s66apreparations of 05Fz and 06F2,366b
and preparation of OaF2 from OF, and 0, 366c have been given. For
OF,, AH,"( -4*06& 2-20 kcal.mole-1) has been redetermined.367aFrom the
mass spectra of 0,F2,03F2,and O,F,, it is deduced that 0,F2and 04F, do
have been estimated [D(FO-OF) = 135; D(F-OOF) -

not exist in the vapour phase,367band the bond dissociation energies in O,F,
18 kcal./mole].
The radical 02Fs6sa is detected by 8.s.r. in photolysed liquid OF2,368bin
02F2,368c, 03F2,36& and 04F2,s6gS and by infrared spectroscopy on photo-
lysis of O n , mixtures in matrices at low temperatures;36*f the radical OF
s58 E. Josefowicz and R. Ladzinska-Kulinska, Roczniki Chem., 1966, 40, 1615.
s6s (a) G. 0 . Doak, G. G. Long, S. K. Kakar, and L. D. Freedman, J. Amer. Chem.
SOC.,1966, 88,2342; ( b ) R. Okawara, K. Yasuda and M. Inoue, BuU. Chem.SOC.Japan,
1966, 39, 1823.
s 6 0 N. Bartlett and I. P. Beaton, Chem. Comm., 1966, 167.
361 D. Samuel and B. L. Silver, Adv. Phys. Org. Chem., 1965, 3, 123.
C. J. Ludman and T. C. Waddington, J . Chem. SOC.( A ) ,1966, 1816.
s8s ( a ) M . Venugopalan and R. A. Jones, Chem. Rev.,1966, 66,133; ( b ) N. Hata and
P. A. Gigukre, Canad. J . Chem., 1966, 44, 869.
s 6 4 (a) I. I. Vol'nov, Russ. Chem. Rev., 1965, 36, 908; ( b ) G. Sosnovsky and J. H.
Brown, Chem. Rev., 1966, 66, 529; (c) W. B. FoxandG. Franz, Inorg. Chem., 1966,5,946.
366 ( a ) N. A. Milas and F. G. Arzoumanidis, Chem. and Ind., 1966, 66; ( b ) R. D.
Youssefyeh and R. W . Murray, ibid., p. 1531.
3 e 6 ( a ) A. G. Streng, Canad. J . Chem., 1966, 44, 1476; ( b ) A. G. Streng and A. V.
Grosse, J . Amer. Chem. SOC.,1966, 88, 169; (c) A. G. Streng and L. V. Streng, Imrg.
Nuclear Chem. Letters, 1966, 2, 107.
8 6 7 ( a ) W. R. Bisbee, J. V. Hamilton, R. Rushworth, T. J. Houser, and J. M.
Gerhauser, Adv. Chem. Ser., 1966,54,215; ( b ) T. J. Malone and H. A. McGee, J . Phya.
Chem., 1965, 69, 4338; T. J. Malone and H. A. McGee, ibid., 1966, 70, 316.
868 ( a ) R. W. Fessenden and R. H. Schuler, J . Chem. Phys., 1965, 43, 2704; R. W.
Fessenden and R. H. Schuler, ibid., 1966,44,434; ( b ) F. I. Metz, F. E. Welsh, and W. B.
Rose, Adv. Chem. Ser., 1966,54,202; (c) P. H. Kmai and A. D. Kirshenbaum,J . Amer.
Chem. Soc., 1965,87, 3069; ( d )F. E. Welsh, F. I. Metz, and W. B. Rose, J. Mol. Spectro-
scopy, 1966, 21, 249; (e) A. D. Kirshenbaum and A. G. Streng, J . A m . Chem. Soc.,
1966, 88, 2434; (f)A. Arkell, ibid., 1965, 87, 4057; R. D. Spratley, J. J. Turner, and
G. C. Pimentel, J . Chem. Phys., 1966, 44, 2063.
View Article Online
has been detected by infrared spectroscopy 36Qa on photolysis of OF, in

noble gas matrices at 4OK but the e.8.r. detection 3139~of 03'on photolysis of
OF2 in CC13F at 77°K has been questioned 888d and the resonance reassigned
to 0,F. The lDI? chemical shift in O,F, is a t unusually low field~;~70 the
bonding in this molecule and in related species containing 02-or NO-groups
has been described s71 in terms of electron donation from the ligand t o the 0,
(or NO) antibonding n-orbitals. Ketones (X,Y)C=O react quantitatively
with F, in the presence of MI? (X, Y = RF or F; M = K, Rb, or Cs) at -78"
to give 372u (X,Y)CFOF; the previously reported preparation 374b by
fluorination of partially fluorinated alcohols gives low yields.
The properties of HCIOc have been reviewed;373the structure of C&O, has
been determined by electron diffraction ;*y4 U.V. spectroscopy indicates that
the complex between (30,- and ClO, is stronger 376 than that between C102-
and UOZ2+.Salts NaXO,F, (X = C1 or Br) are obtained 378 on dissolving
NaXO, in cold 40% HF.
Sutphur. Further theoretical studies of the d-orbitals of S have been
made;377athe relationship between chemical binding and X-ray spectra of S
compounds has been discussed.877 b Ultraviolet and vibrational spectra of
R,S, have been used in a theoretical analysis of the bonding in these com-
p o u n d ~ the ; ~ ultraviolet
~~~ spectra of aromatic S-derivatives,378band the
n.m.r. spectra of S ylids 378eand of ap-unsaturated sulphonium ~ a l t s ,have s~~~
been discussed in relation to possible d-orbital participation ; the e.8.r.
spectra of the radical-anions of diphenyl sulphone and di-p-tolyl sulphone
indicate strong ring interactions, perhaps through d-orbitals of sulphur.87*
The reactions of atomic S have been reviewed,~7@~ and dissociation energies
of diatomic molecules of the elements S-Te collected.379b From the n.m.r.
spectra of some ring compounds of S and Pt, it is deduced that inversion at S
is slow; 880a evidence has been presented to indicate that racemisation of
ButEtMeS+C1- involves inversion and is independent of heter0lysis.380~
Elemental forms of S containing S, and S ,, units have been described;SBl*
a review has been published of the synthetic use of the reactions between
86B (a)A. Arkell, R. R. Reinhard, and L. P. Larson, J . Amer. Chern. Soc., 1965, 87,
1016; ( b ) F.Neumayer and N. Vanderkooi, Inorg. Chem., 1965, 4, 1234.
37* N.J. Lawrence, J. S. Ogden, and J. J. Turner, Chem. Cmm., 1966, 102.
871 R. D. Spratley and G. C. Pimentel, J . Amer. Cham. SOC.,1966, 88, 2394.
s78 (a)J. K. Ruff, A. R. Pitochelli, and M. Lustig, J. Amer. Chem. SOC.,1966, 88,
4531; ( b ) J. H.Prages and P. G. Thompson, ibid., 1965, 87, 230.
873 G.S. Pearson, Adu. Inorg. C h m . Radiochem., 1966, 8, 178.
8 7 4 B. Beagley, T r a m . Paraday Soc., 1966, 61, 1821.
8 7 6 C . Gordon and F. Emmenegger, Inorg. Nuclear Chem. Letters, 1966, 2, 395.
GF. Mitra, 2. anorg. Chem., 1965, 540, 110.
8 7 7 (a) C. L. Bendazzoli and C. Zauli, J. C h .SOC., 1965, 6827;D. P.Crag and T.
Thirunamachandrm, J . Chern. Phys., 1966, 45, 3355; ( b ) D. W.Wilbur, U.8.Atomic
Energy Comm., 1966, UCRL-14379.
(a)S. D. Thompson, D. (3. Carroll, F. Watson, M. O'DonnelI, and S. P. McGlynn,
J . Chem. Phys., 1966, 45, 1367; ( b ) L.Goodman and R. W. Taft, J. Amer. Chem. SOC.,
1966,87, 4385;(c) K.W.Ratts, Tetrahedron Letters, 1966, 4707; ( d ) M.C. Caserio, R. E.
Pratt, and R.J. Holland,J . Amer. Chem. SOC.,1966, 88, 5747; ( e ) E.T. Kaiser, M. M.
Urberg, and D. H. Eargle, ibid., p. 1037.
8 7 8 (a)H. E. Gunning, Elem. &u@hur, Cham. Phys., 1965, 265; (b) J. Drowart and
P. Goldfinger, Quart. Rev.,1966,20, 646.
8 8 0 ( a ) E. W. Abel, R. P. Bush, P. J. Hopton, and C. R. Jenkins, Chem. Comm.,
1966, 5 8 ; (b) D.Darwish and G. Tourigny, J. Amer. Chem. SOC.,1966, 88,4303.
881 (a)M. Schmidt, Elem. Sulphur, Chern. Phys., 1965, 327; ( b ) H.Schumann and
View Article Online
D O W N S , EBSWORTH A N D T U R N E R : T H E T Y P I C A L ELEMENTS 179
elementary S, Se, or Te and R,MLi (M = Si, Ge, Sn, or Pb).381b Acid-base

concepts in the solvent liquid S have been discus~ed,38~~ and the solubilities
of CS2 and of SO, 3818 determined; the infrared 381f and n.m.r.384
spectra of H2S in liquid S suggest that an equilibrium between H2S, S and

H2S, is set up. The action of Na or K atoms on H2Sat 77°K gives s82a H2S-.
Salts R4N+SH- have been obtained S82b from their strongly conducting
solutions in liquid H,S; H2S is weakly bound to the anions, the hydrogen-
bond energy being estimated as ca. 5 kcal./mole,ss2b and as > 7
kca1./mo1e,Sg2c by different workers. Anions BX,SH- (X = F, Cl, Br, Et),
(SiF4)2S2-,GeF4(SH),,-, SiC14S2-,and SiC14(SH)2-have been prepared in the
~ ~ , the reaction with B2Hswas more complicated.
same s o l ~ e n t , 3 ~though
Exchange 382f of labelled S between solvent H2S and S, CS2, Me,S, or EtSH
is slow in neutral solution; in the presence of Me3N, exchange is fast with
As,S,, &2s,, Sb,S,, CS,, and S, moderately fast with P2s,, and very slow
with EtSH. Dilution shifts in the n.m.r. spectra of RSH in CCl, and other
solvents have been interpreted in terms of an equilibrium between mono-
mers and dimers, and the equilibrium constants calculated; indications of
the formation of (PhSH), in CCl, are put down to changes in solution aniso-
tropy with c o n c e n t r a t i ~ n . ~
The ~ and products of autosidation of
~ ~rate
dilute, aqueous, acidic sulphide or polysulphide solutions depend s823(on the
concentration of HS-. A method for the large-scale synthesis of S,Cl,
(x =3-6) from H2S, (y = 1-4) and SzC12(z = 1-2) has been described.883
Correlations between the ( S 4 ) bond distance and the activation energy
for displacement reactions by nucleophile~,~84~ and between the (S-S) dis-
tance and the dihedral 5~ngle,38~~ have been remarked. Alkali metal
fluorides react with SCF, to give F3CSC(S)Fand (CF,S),CS, and the forma-
tion of SCF,- was not detected;s855 oxidation 385b of MeSCF, with HNOs
or with H202 in acetic acid gives MeS(O)CF,. The peduorothioketen
(CF,),C=C=S has been obtained 386 by heating the dimer produced by the
Me,/---,
+ Me S
Me,+ +/Me
S - CH2 -. S , ;S - CHI - s: R N
$
H '
~C *SMe
4
M k Me Me Me N-N
(3 5) (36) (3 7)
M. Schmidt, Angew. Chem., Inkmat. Edn., 1965, 8, 1007; ( c ) T. K. Wiewiorowski m d
F. J. Touro, J. Phya. C h . , 1966, '70, 3528; ( d ) F. J. Touro and T. K. Wiewiorowski,
ibid., p. 3531; ( e ) F. J. Touro and T. K. Wiewiorowski, dbid., p. 3534; (f)T.I(.Wiewio-
rowski and F. J. TODO,ibid., p. 234; ( g ) J. B.Hyne, E. Muller, and T.I(.Wiewioromki,
ibid., p. 3733.
(a)J. E. Bennett, €3. Mile, and A. Thomas, Chem. C m . , 1966, 182; ( 6 ) J. D.
Cotton and T. C. Waddington, J . Chem. SOC.( A ) , 1966, 785; ( c ) D. H. McDaniel and
W. G. Evans, Inwg. Cbm., 1966, 6, 2180; ( d ) J. D. Cotton and T. C. Waddington,
J . C h . SOC.( A ) , 1966, 789; (e) J. D. Cotton and T. C. Waddington, ibid., p. 793;
(f)J. R. Mickelsen, T.H. Norris, and R. C. Smith, Inorg. Chern., 1966, 5, 911; (9) 8. H.
Marcus and S. I. Miller, J . Amer. Chem.SOC.,1966,88,3719; (h) J. W. Bowem, M. J. A.
Fuller, and J. E. Packer, Cbm. and Ind., 1966, 65.
383 F. Fehhr, J. Grobell, and F . R.Minz, 2.anorg. Chem., 1966, 343, 146.
m4 (a) R. E. Davis, J. B. Lonis, and A. Cohen, J . Amer. Chem. SOC.,1966, 88, 1
( b ) A. Hordvik, Acta Chem. S c a d . , 1966, 20, 1885.
(a) A. Haw and W. Klug, Angsw. Chem., Internat. Edn., 1966, 5, 845; (b) L. M.
Yagupol'akii and A.-G. Panteleimonov,J . Qen. C h m . (U.S.S.R.),1965, 35, 1123.
M. S. Rmsh, C h m . Comna., 1966, 577.
View Article Online
180 INORQANIC CHEMISTRY
action of SF, and HF on (34). The reaction between Me,0+BF4- and

(MeS),CH, gives s87a the bis(fluoroborate)of (35), and this when treated with
KOH in MeOH gives the fluoroborate of (36). A compound formulated from
chemical and spectroscopic evidence 887b as MeS0,CH: S0,NMe3 has been

obtained from the reaction between Me3N and MeS0,Cl in MeCN a t -40'.
The vapours of CS, and SO, do not react below 400", but in the condensed
phase the ultimate product of reaction is polymeric material containing S
chains with CS and CO groups.388
A new MO description of the N4S4molecule indicates that the role of the
d-orbitals of S is significant but not large, and predicts the formation of
miom N4SP- ( f i = 1-4) with delocalised n-electrons.389 The infrared
spectrum of SP, is consistent with symmetry (planar ring), though CZb
symmetry (puckered ring) cannot be excl~ded.~~O The crystal symmetry
of S,NH has been determined.391 The G s t product of the action of S,C1,
on NH,has been identsed 392 as monomericNSCl. The free acid H(H,NCS,)
has been obtained 393 from the ammonium salt and conc. HCl a t 0". The
molecules (NSC1)3394a and a-(NSOCI),Sg4bin the crystal are both in the chair
form, with axial C1 atoms; crystalline S,N,Cl, consists s94c of puckered
S,N,Cl+ rings and C1- ions. The action of RC(:NOH)Cl on H,N*NH-CS2Me
gives s9s (37). The chemistry of the compounds formed by S4N4 with metals
has been reviewed.396 The structure of the compound C,H,N,S, formed
from Me,S and H,NCl, has been reassigned 397 as Me,S(NH), rather than
Me2SNH+*NH-, from its mass spectrum and reactions; with Br,,
Me,S(N€I)NBr is produced, with gives [HNSMe,*NPPh,]+Br- with PPh,.
When AgF and S are heated to 140°, blue SF, is f ~ r m e d ; the
~ ~ gcompound,
characterised by analysis, is volatile a t -78" in vmuo, reacts quantitatively
with HI to give iodine, and with KBr forms SBr,. In acetone, SCl, reacts
with AgNO, or KI to form CISNO, or CISI; with excess of AgNO,, the un-
stable S(N03),may be formed. The conductometric behaviour of the solu-
tions implies ionisation of the S cornpound~.~9~~ In the absence of base,
C5Hl,,NSCl reacts 399b with (A = EtO, 4-Me2NC,H4,4-Mec,H4s) to give
A@, but in the presence of pyridine reaction with AH (A = EtO, 4-MeC,H4S)
gives C,H1PSA, decomposed by acid. The angle a t S in crystalline S(CN),
is 95.6', and the (SCN) groups are (within error) linear.399eAt 160"and low
8 8 7 (a) C . P. Lillya and P. Miller, J . Amer. Chm. SOC., 1966, 88, 1669, 1560; (b) Q.
Opitz, & Kleeman,
I . D. Biicher, G. Walz, and K. Rieth, Angew. Chern., Int9lrzat. Edn.,
1966, 5, 694; G. Opitz and D. Bucher, Tetrahedron Letters, 1966, 6263.
R. Steudel, 2. anorg. Chmn., 1966, 346, 265.
a * 0 A. G. Turner and F. S . Mortimer, Inorg. C h m . , 1966, 5, 906.
J. R. N. Warn and D. Chapman, Spectrochim. Acta, 1966, 22, 1371.
a O 1EL Garcia, C m p t . rend, Ser. C., 1966, 283, 1362.
M. Becke-Goehring and D. Schliifer, 2.Naturforsch., 1966, 21b, 492.
898 #. #attow and V. Hahnkamm, Angew. Chem., Inhmat. Edn., 1966,6, 316.
m 4 ( a ) G. A. Wiegers and A. Vos, Acta Cryst., 1966, 20, 192; (b) A. C. HazeU, 0.A.
Wiegers, and A. Vos, {bid., p. 186; (c) A. Zalkin, T. E. Hopkins, and D. H. Templeton,
Inwg. C h . ,1966, 5,1767.
8 0 6 A. Dornow and K. Fischer, Chem. Ber., 1966, 99, 72.
1106 J. Weiss, Forhchr. C h . Porsch., 1966, 5, 635.
8 9 7 R. Appel, H. W. Fehlhaber,D. Hiinssgen, and R. Schollhorn, Chem. Ber., 1966,
99, 3108.
8 8 8 D. K. Padma and S. R. Satyanarayana, J . Inorg. Nuclear Cbm., 1966,28, 2432.
0 9 9 (a)$. N. Nabi and M. S. Amin, J . Ohem. SOC.( A ) ,1966, 1018; ( b ) L. Almaai and
A. Hantz, Chsm. Ber., 1966, 99, 3288; (c) K. Emerson, Ada Cq8t., 1966, 21, 970.
View Article Online
D O W N S , E B S W O R T H A N D T U R N E R : T H E T Y P I C A L E L E M E N T S 181
pressures, SOC1, and Ag2Sreact together to give S,O (97% purity); the
compound is monomericas vapour, and (apparently)in dilute sohd solution in
SO2 (yellow at -196"), but when condensed alone it forms red polymeric
material at this temperature, and the condensate gives an e.s.r. spectrum a t

-150". Neither SOC1, nor S,O forms compounds with BF, a t -150", but
both give 1 : 1 adducts with Me,N that may be sublimed in vmuo and are
stable a t room temperature.mb Work has continued on the adducts of SO2
with transition metals.401 Sulpholan forms a 1 : 1 adduct with BF, but not
with PF, (though in the latter case there is evidence of reaction).a2
The action of NO2 on HS0,Cl gives HS,O,NO; this or related com-
pounds 4 0 3 = ~b are formed in the reactions between N02C1and HSO,Cl, and
between N02C1 and SO,. The dissociation constant of methanesulphonic
acid from Raman spectra is m. 73 molefitre, so the acid is stronger than
nitric acid.404 The thermal decompositions of sulphamic acid 4055 and of
sulphamide 405b are complex processes; from the latter, a number of new
S-N oxyacid derivatives has been isolated. The action of KF in CH&N on
(NSOCl), gives 406 (NSOF),, of which the pure cis-isomer has been isolated;
it reacts with PhLi to give Ph,PO,S,N,, and with benzene in the presence of
AlCl, to give two forms of (NSOPh),. Chlorination of AgN(SO,F), gives 407
ClN(SO,F),, which photolyses to form (FSO,),N,, adds to CO, ClCN, and
BrCN, and gives a salt of NO+ with NO. Cryoscopy in HS0,F has been
described,408aand the equilibria betyeen H20(giving HF and H2S04)or
KNO, (giving K+, NO,+, and H,O+) and the solvent have been investigated
by cryoscopy and conductometry.408b Values for lSF chemical shifts in
OS0,F-derivatives have been collected.*Og
Recent progress in sulphur-fluorine chemistry has been re~iewed.~lO~
Aluminium chloride reacts 41°b with R,N: SF, to give R,N: SCl,, which with
Ag20 forms RFN:S: 0. Treatment of Si(NCO), with SF40in the presence
of BF, gives OSF,NCOF, which forms an adduct with Csl?; the action of X,
(X = F or Cl) on this adduct gives O:SF,:NX, decomposed by ultraviolet
irradiation. The preparation of SNClF, (probably SF,:NCl) from NSF and
C1, in the presence of CsF, or from SF,NCOF, CsF, and C1, in a static system,
is described; an unstable material, perhaps SF,NBr, was obtained from
NSF, CsF, and Br,, but attempts to make SF2NF were u n s u c c e ~ s f u l . ~ ~ ~
The new compound SF5NH, has been prepared from NSF, and KE a t room
400 P. W. Schenk and R. Steudel, 2.anorg. C h . , 1966, 342, ( a ) p. 253; ( b ) p. 263.

401 F. A. Hartman and A. Woicicki, J . Amer. Chem. Soc., 1966, 88, 844; L. Vasks
and S. S. Bath, ibid., p. 1333.
( 0 2 J. G. Jones, Inorg. Chem., 1966, 5, 1229.
40s (a) M. Wartel, S. Noel, and J. Heubel, Compt. rend., Ser. C, 1966, 862, 921;
( b ) K. Stopperka and V. Grove, 2. anorg. Chem., 1966, 347, 19.
404 J. H. R. Clarke and L. A. Woodward, Trans. Paraday SOC., 1966, 62, 2226.
4 0 6 (a)W. Wanek, 2. Chem., 1966,6,423; (6) K. Nara, M. Nakagaki, 0. Manabe, and
H. Hiyamct, Hog0 Kagaku Zassha', 1966, 69, 20.
'06 T. Moeller and A. Ouchi, J . Inorg. Nuclear Chem., 1966, 28,2147.
4 0 7 J. K. Ruff, I w r g . Cherra., 1966, 5, 732.
4 0 8 (a) R. J. Gillespie, J. B. Milne, and R. C. Thompson, Inorg. Chem., 1966,5,468;
( b ) R. J. Gillespie, J. B. Milne, and J. B. Senior, ibid., p. 1233.
40B F. A. Hohorst and J. M. Shreeve, Inorg. C h . , 1966, 5, 2069.
410 ( a ) S. M. Williamson, Progr. Inorg. C h m . , 1966, 7 , 39; ( b ) M. Lustig, Inorg.
Chem. ,1966, 5, 1317; (c) J. I(.Ruff, &id., p. 1787.
View Article Online
temperature;411afluorination of S4N4with *In F2/N2a t O", or treatment 4110

of NSF, with SF4 in the presence of BF,, gives SF,N:SF,. The adduct
(Me3N)&3F6Cl,formed a t low temperatures, decomposes to SF4 and
(MeaN),CIF on warming to room temperature ;41Zuthe compound MeNSFa

is obtained from MeNH, and SF,C1 or SF,, and the latter process also gives
(MeN),S. Irradiation 412b of a mixture of SF,C1 or SF, with ClN(CF,), leads
to the formation of (CF3),NSF,. The acceleration of the decomposition of
But202by sF6has been put down to the attack of Me radicals on SF,, and the
formation of MeF has been detected!ls4 Contrary to previous reports, no
reaction was detected 413b between SF, and HI.
Selenium. The chemistry of Se, Te, and Po has been described in a book.414
The thermodynamics of the direct reaction between Se and H,, giving SeH,,
do not after all show any anomaliea.*l5 In Me,Se the angle a t Se has been
found by microwave spectroscopy 416 to be 96'11' & 10'. The action of
ammonia on Ph,SeCl, in CH,C12 gives a white crystalline solid, formulated as
[Ph,Se:N:SePh,]+Cl-, in which the C1 ion can be exchanged for other
anion^;^^'^ N,Se, has the same cage-likestructure as N,S,, but the packing in
the lattice is The chemistry of inorganic SeO-compounds has
been r e v i e ~ e d . 4 ~Treatment
~~ of SeOC1, with NaOOCCH, or (COOAg),
gives 4lSb the SeO-derivative of the organic acid; the oxalate is monomeric
in dioxan, and is described as containing 3-co-ordinated Se. The action of
MX on SeOX, (&I = alkali metal;, X = IF, C1, OMe, OEt) gives ,ls0
M+[SeOX,] - ; the alkoxides in alcohol are almost completely dissociated into
Se(OR), and OR- and are decomposed by CO,, giving SeO(OR),. Several
cornplexea of metals with Ph,SeO have been prepared.418d Selenium trioxide
dissolves unchanged in POCl, or S02C1,, and in solution is reduced by SOCI,
or PCl,, the products depending on the s o l ~ e n t . 4 ~ ~Crystalline
a com-
pounds 419b SeO,,I,OS and I,0,,2Se03,H,0 have been obtained from SeO,
and I,O, or HIO,; polyselenate anions and protonated speciea have been
detected4204 by Raman spectroscopy in solutions of SeO, in anhydrous
H,Se04, and polyselenates have been prepared from SeO, and alkali metal
carbonates or ~elenates.4~0bAcidity functions of selenic acid have been
determined, using indicators.42w The species formed by dissolving Sea, in
'11 (a)A. F. ClifTord and I;. F. Duncan, Inorg. C h . , 1966, 5, 692; (b) B. Cohen,
T. R. Hooper, and R. D. Peacock, Chern. Cornrn., 1966, 32; (c) A. F. Clifford and J. W.
Thompson, Inorg. Chern., 1966, 5, 1424.
41a (a) B. Cohen and A. G. MacDiarmid, J. Chern. SOC. ( A ) , 1966, 1780; ( b ) R. C.
Dobbie, ibid., p. 1555.
nS(a) L. Batt and F. R. Chickshank,J. Phys. Chm., 1966, 70, 723; (b) J. R. Case
and H. L. Roberts, 1n:;g. Chem., 1966, 5, 333.
K. W.Bagnall, The Chemistry of Se, Te and Po," Elsevier, 1966.
416 J. R. Rawling and J. M. Toguri, Canad. J. Chern., 1966,44,461.
410 J. F. Beecher, J. Mol. Spectroscopy, 1966, 21, 414; K. H. Linke and F.
Lemmer, 2. a w g . C h . ,1966, 345, 203.
(a)R. Appel and (3. Buchler, 2. anorg. Chem., 1966,848,176; (b)H.Bhighausen,
T. von Volkmann, and J. Jander, Ada Cqst., 1966,21, 671.
418 ( a ) R. Paetzold, Fortschr. Chem. It'orsch., 1966, S, 690; ( b ) R. Pmtzold, 2.Chem.,
1966,6,72; (c) R. Pmtzold and K. Aurich, ibid., p. 152; ( d ) R. Pmtzold and P. Vordank,
2.anorg. Chm., 1966, 347, 294.
'lS (a) E. Class, Experientia, 1966, 22, 133; (b) G.Kempe and D. Robus, 2. Chem.,
1966, 5, 394.
4 1 0 ( a )R. Paetzold and H. Amoulong, 2. arz.org. Chem., 1966, 843, 70; (b) a. Kempe
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D O W N S , DBSWORTH A N D T U R N I R : THE T Y P I C A L ELEMENTS 183
liquid Se have been described in chemical terms42l 8s 2Se-t. and 2C1-;

crystalline Me,SeI contains 422a ion-pairs of I- and pyramidal Me,%+.
There is no evidence in the infrared spectra of salts of SeXe2-or TeX,,- of
distortion of the
Tellurium. In crystalline [(MeO),P(S)S],Te, the co-ordination a t Te can
be regarded as square-planar, with STeS angle of 95.7" and weak Te-S inter-
actions with two other S atoms:423a the crystal of Te(tu),(HF,),
(tu = thiourea) contains a binuclear cation, with Te in a distorted square-
planar and in PhTe(tu),Cl the Te atom in the PhTe(tu)%+
ion is in a square-planar environment with one position ernpty.4,3c A review
of the oxides and oxyacids of Te has The infrared spectra of
TeX, (X = C1, Br, I)are consistent with the formulation of the compounds as
TeX,+X-, and no evidence was obtained for the presence of molecules in the
s0lid;~~5" the compounds MTeF5 (M = alkali metal, NH4+, pyH+) are
formulated on the basis of their vibrational spectra and the conductivity and
molecular weight of the pyridinium derivative in methanol or pyridine as
salts, with Te in a square pyramid of F atoms.425b The anions TeC1,2-
[in (NH,),TeCI,J 426a and TeBr,2- [in (NH4)2,Cs,TeBr,] are undistorted,426b
at least to a considerable degree of precision.
Group VII.-Solid-state galvanic cells have been used 427 to determine
AG," for several fluorides. The chemistry of bromine has been described in a
book 42ga and a re vie^.^,^^ The oxidation of I, by different amounts of
S206F2in fluorosulphuric acid has been investigated spectroscopically, and
using measurements of conductivity, molecular weight, and magnetic suscep-
tibilit~:"~ with excess of S20,F2,I(So,E"),is f ~ r m e d ; ~with
* ~ a I, : S206P2of
1 : 1 and 2 : I, the species I,+ is prod~ced.4~~* The U.V. spectrum of I,+
is identical 429c with that of the species obtained on dissolving 1,or IC1 in 65%
oleum or I, in IF5 and previously attributed t o I+. The fist complex salts
have been prepared 430 containing halogen/nitrate anions [Me,NI(NO,),,
Me,NI(NO,),; Me,NBr(NO,),]; the preparation of I(SCN),- by oxidation
of 12/SCN- solutions has been c0nfirmed,~31~ and infrared spectroscopyshows
that in M(I>~),(NCS),(I~)~ [M = CO(II), Ni(rr)] one iodine molecule is bound
and D. Schmitt, 2.Chem., 1965,5,427; ( c ) D. H. McDaniel and L.H. Steinert, J . Amer.

c h .soc., 1966,88,4826.
4a1 M. Lundkvist and L. G. Sillh, Acta Chem. Scund., 1966, 20, 1723.
4 2 8 (a)H. Hope, Actu Cryst., 1966,20,610; (b) N. N. Greenwood and B. P. Straughm,
J . Chem. SOC.( A ) , 1966, 962.
P a s (u)H. Husebye, Acta Chem. Scand., 1966, 20,24; ( b ) 0. Foss and S. Hauge, ibid.,
1965,19,2395; (c) 0. Foss and K. Maroy, ibid., 1966, 20, 123.
4 2 4 W. A. Dutton and W. C. Cooper, Chem. Rev., 1966, 66, 657.
4a6 (a)N. N. Greenwood, €3. P. Straughan, and A. E. Wilson, J . Chem. SOC.( A ) ,
1966, 1479; (a) N. N. Greenwood, A. C. Sama, and B. P. Straughm, J . Chem. SOC.( A ) ,
1966, 1446.
426 (a)A. C. Hazell, Ada C b m . Scud., 1966,20,165; ( b )A. K. Das and I. D. Brown,
Cunad. J . Chem., 1966, 44,939.
4 * 7 R. J. Heus and J. J. Egan, 2.phys. Chem. (Frankfurt),1966, 49, 38.
( a ) " Bromine and its Compounds," ed. Z . E. Jolles, Ernest Benn Ltd., London,
1966; ( b ) V. A. Stenger, Angew. Chem., Internact. Edn., 1966, 5, 280.
4 2 s R. J. Gillespie and J. B. Milne, (a)Inorg. Chem., 1966, 5, 1236; ( b ) Chern. Comm.,
1966, 158; (c) Inorg. Chem., 1966, 5 , 1577.
4 3 0 M. Lustig and J. K. Ruff, Inorg. Chem., 1966, 5, 2124.
View Article Online
to one thiocyanate Many other iodine complexes have, been

studied; infrared spectra suggest 432a that in the following complexes the
order of strength is pyI, < pyIBr < pyIC1; in dioxan, I,/trialkylamine
complexes are probably ion-pairs;432bthe complexes between I, and amino-

boranes are probably bound by 1,-N o-bonds rather than by n-interactions
from the B-N bonds;135a U.V. spectra give evidence for the persistence of
1 : 1 complexes between I, and Et20or benzene in the vapour phase,432~m d
py,ZI, has been detected in the gas phase by mass spectrometry.-432d The
role of solvent has been e m p h a ~ i s e d , Q
and
~ ~gas-solid
~ chromatography em-
ployed.a2' Ion-pairs and complexes of I- have been investigated by u . ~ .
spectros~opy:~~ and evidence has been obtained for the formation of the
complex I * * * I-H on photolysing EtI in a hydrocarbon matrix434 at
77°K. Organic polyvalent iodine compounds have been reviewed.435 Mass
spectra have given evidence 436 for the formation of HAt, MeAt, AtI, AtBr,
and AtCl, but there was no indication of At,.
The lH- and l9F-n.m.r. spectra of solid KH,F3 indicate that the H-bond
potential function is not symmetrical 437 (cf. HI?,-). The preparations of 43g0
R,N+(FHX)-(X = Cl, Br, I) from R,NX and gaseous HF and of 43gb Me,N+
(CIHN0,)- are confirmed by infrared spectroscopy. The potential function
in R4N+HCl,- (It = Et, Pr*, n-Pent) is apparently symmetric; infrared
spectra 4390 are said to indicate that in M+HC12- (M = Cs, Me4N, Bun4N)
the potential function has a single asymmetric minimum, but a single
chlorine NQR signal was observed.439b The compound obtained from
gaseous HC1 and saturated aqueous CsCl is shown by X-ray diffraction to
be CsC1,1/3(H30+.HCl,-) and hence the first measurement of the Cl-Cl
distance in a bichloride is obtained.*39c A photolytic preparation of ClF,
a t room temperature and one atmosphere pressure has been des~ribed.~40
The pentagonal bipyramid structure of IF, has been codirmed?41
Vibrational spectra suggest that the ClF4- ion is square-planar in the Rb
and Cs salts, but not 442a in NO+C1F4-; that C1,- is linear and symmetric in
the Et4N+, Prn4N+,and Bun4N+ ~ a l t s ; ~ 4that 2 ~ the C1,- ion is present in
a1( a )C . Long and D. A. Skoog, Inorg. Chem., 1966,5,206; ( b )D. Forster and D. M. L.
Goodgame, J . Chem. SOC.( A ) ,19G6, 170.
r 3 z (a) S. G. W. Ginn and J. L. Wood, Tram. Paraday SOC.,1966, 62, 777; ( b ) K.
Toyada and W. B. Person, J . Amer. Chem. SOC.,1966, 88, 1629; (c) F. T. Lang and
R . L. Strong, ibid., 1965, 87, 2345; ( d ) R. Cahay and J. E. Collins, Nature, 1966, 211,
1175; ( e ) R. S. Drago, T. F. BoIles, and R. J. Niedzielski, J . Amer. Chem. SOC,,1966,
88, 2717; (f)R. J. Cvetanovi6, F. J. Duncan, W. E. Falconer, and W. A. Sunder, ibid.,
p. 1602.
433 M. J. Blandamer, T. E. &ugh, and M. C. R. Symons, Trans. Paraday SOC.,
1966, 62, 28G, 301.
4 3 4 D. Timm, Acta Chem. Scand., 1966, 20, 2219.
4 3 5 D. F. Banks, Chem. Rev.,1966, 66, 243.
IS6 E. H. Appelman E. N. Sloth, and M. H. Studier, Inorg. Chem., 1966, 5, 766.
43' R. Blinc, Z . Trontelj, and B. Volavgek, J . Chem. Phys., 1966, 44, 1028.
( a )6.C . Evans and G. Y.-S. Lo,J. Phys. Chm., 1966,70,543; ( b ) J,A. Salthouse
and T. C. Waddington, J . Chem. SOC.( A ) ,1966, 28.
43O ( a ) J . C. Evans and G. Y.-S. Lo, J . Phys. Chem., 1966,70, 11; ( b ) J. C. Evans and
G. Y.-8. Lo, ibid., p. 2702; ( c ) L. W. Schroeder and J. A. Ibers, J. A w . C h . SOC.,
1966,88, 2601.
4 4 0 R. Gatti, R. I;. Krieger, J. E. Sicre, and H. J. Schumacher, J. Inorg. Nuclear
Chem., 1966, 28, 655.
4 4 1 H. B. Thompson, end L. S . Bartell, Trans, Amer. Crgst. ASSOC., 1966, 2, 190.
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DOWNS, E B S W O R T H A N D T U R N E R : THE T Y P I C A L ELEMENTS 185
acetonitrile solution when 442b C1, : C1- > 1; that the ClBr,- ion has the
linear arrangement 442c ClBrBr-; and that the ions I,Cl,-, 12C12Br-, and
12ClBr2-are present 442d in the 1 : 1 adducts of BHIC1, (B = pyridine-type
base) with IC1 and IBr and of BHIBr, with IC1. X-ray diffraction shows
that Cs1,Br is isostructural with CsI,, and that the BrII- ion is n ~ n - l i n e a r . ~ ~ ~
The stability constants of Br2C1- and BrC1,- in aqueous solution have been
determined from redox potentials ;Ireaa the stability constants of Br3- and
Br,- are sensitive to changes in ionic strength;444b the reaction in liquid HC1
of halogens and interhalogens with halide lion has been studied conducto-
rnetri~ally.4~~ In KICl, and KICl,, Mossbauer (12'1) spectroscopy
favours 446 a model with delocalized orbital bonding and with little or no
contribution from the s-orbitals of the I atoms. The adduct BrF3,BF3is said
to be stable only 447a up to -80" and to melt with decomposition 447b at
180"; infrared spectra suggest that this adduct may be represented 447b by
BrF,+ BF4-, but that 2BrF3,GeF4does not consist of BrF,+ and GeFe2-
ions.447a Iodine trifluoride forms 1 : 1 adducts 448 with BF,, AsF5,and SbF,
which may contain the species IF,+.
4 4 2 (a) K. 0 . Christie and J. P. Guertin, I n o r g . Chem., 1966, 5, 473; (b) J. C. Evans
and G . Y.-5. Lo, J . Chem. Phys., 1966, 44, 3638; (c) J . C. Evans and G. Y . - S . Lo, ibid.,
1966, 46, 1069; ( d ) Y. Yagi and A. I. Popov, Inorg. Nuclear Chem. Letters, 1965, 1, 21.
4 4 3 G. B. Carpenter, Acta Cryst., 1966, 20, 330.
4 4 4 (a)R. P. Bell and M. Pring, J . Chem. SOC. ( A ) ,1966,1607; ( 6 ) V. E. Mironov and
N. P. Lastovkina, Rws. 3. Inorg. Chem., 1965,10,687; V. E. Mironov and N. P. Lastov-
kina, {bid., 1966, 11, 314.
4 4 5 J. A. Salthouse and T. C. Waddington, J . Chem. SOC.( A ) ,1966, 1188.
4 4 6 G. J. Perlow and M. R. Perlow, J . Chem. Phys., 1966, (C), 45, 2193.
4 4 7 ( a ) D. H. Brown, K. R. Dixon, and D. W. A. Sharp, Chem. Comm., 1966, 654;
( b ) M. S. Toy and W. A. Cannon, J . Phys. Chem., 1966, 70, 2241.
4 4 8 M. Schmeisser and W. Ludovici, 2.Naturforsch., 1965, 20b, 602.
View Article Online
4. T H E TRANSITION ELEMENTS
By F. E. Mabbs and I). 3. Machin

(Chembtry Department, Ths Uniuersity, Mancheater, 13)
As in previous years, transition-metal chemistry will be reviewed by dividing

the elements into groups. Compounds will be discussed generally in order
of increasing oxidation state of the metal. Papers dealing with elements
from a number of groups will usually be mentioned only once. It has been
necessary, once again, to omit any reference to the large amount of work
being published in the field of solvent extraction of metals. It is impossible
to cover this field adequately in the space available.
General reviews which have appeared during the year include a dis-
cussion of five-co-ordination, and the chemistry of compounds containing
metal-atom c1usters.l Schiff base and /I-keto-amine complexes, nitric oxide
compounds of the transition-elements, and 18-keto-enolate complexes have
been considered,2as well as the Cotton effect in co-ordination compounds.s
Scandium and the Lanthanides.-Two equilibrium compounds, 3NaFScFs
(cryolite-type) and NaPScF, (hexagonal), have been found 4 in the sodium
fluoride-scandium fluoride system. The ternary oxide MgSc,O, has been
prepared a t temperatures above 2000"~. Its structure is similar to that
of CaSc,O, and CaFe,O,. Hydrolysis studies of scandium(m) perchIorate
by means of ultracentrifugation have established the species present.
The nature of solutions of europium and ytterbium in liquid ammonia,,
discussed last year, has been confirmed by studies of their electronic spectra.'
Phase studies 8 of the lanthanide sesquioxides at very high pressures and
temperatures have been described, and the tungsten bronzes lb&.lWO, p:e-
pared 9 for thirteen lanthanides; their magnetic properties were also dis-
cussed. Lanthanide titanates MTiO, can be prepared for a number of
lanthanides, M. The formation of oxide-carbidesNdC,O, and MC,O (M = Y,
Sc) has been observed.ll The published structure of lanthanum(m) fluoride
has been shown to be incorrect. The corrected structure 1 2 has nine nearest-
neighbour fluoride ions. The lanthanide elements and their nitrides 13 have
interesting magnetic properties.
E. L. Meutterties and R. A. Schum, Quart. Rev., 1966, 20, 246; F. A. Cotton

aid., p. 389.
a R. H. Holm, G.W. Everett, and A. Chakravorty, Prog. I w g . Chem., 1966, 7 ,
83; B. F. G. Johnson and J. A. McCleverty, ibid., p. 277; J. P. Fackler, ibid., p. 361.
3 R . D. Gillard, Prog. Inorg. Chem., 166, 7 , 216.
4 R. E. Thoma and R. H. Karraker, Inorg. Chem., 1966,5, 1933.
H. Miiller-Buschbaum, 2.anorg. Chem., 1966, 343, 113.
6 J. Aveston, J. Chem. Soc. ( A ) ,1966, 1699.
D. S. Thompson, D. W. Schaefer, and J. S . Waugh, Inorg. Chem., 1966, 5, 326.
* H. R. Hoekstra, Inorg. Chem., 1966, 5, 764.
0 W. Ostertag, Inorg. Chem., 1966, 6, 768.
1 0 H. Holzapfel and J. Sieler, 2. unorg. Chm., 1966, 343, 174.
11A. D. Butherus, R. B. Leonard, G . L. Buchel, and H. A. Eick, Inorg. O M . ,
1966, 5, 1667.
la A. Zalkin, D. H. Templeton, and T. E. Hopkins, Inorg. Chem., 1966, 5, 1466.
18 D. P. Schumecher and W. E. Wallance, Inorg. Chem., 1966, 6, 1663.
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M A B B S A N D M A C H I N : THE T R A N S I T I O N E L E M E N T S 187
New preparations for praesodymium and neodymiun(m) azides,l* a
number of alkoxides,l5 and cyclopentadienyl complexes l6 have been des-
cribed. The mass spectrum of caesium tetrakis-hexafluoroacetylacetonato-
yttrium(m) shows l7that the ion Cs~(acacF,),]+is particularly, and un-

expectedly, stable. Some 1,lo-phenanthroline, dibenzoylmethane, and
2,2’-bipyridyl complexes have been reported, and their fluorescent pro-
perties discussed.ls Tris-chelates of y-isopropyltropolone with lanthanide
ions are associated, leading to seven-co-ordinated structures. Monothio-
tropone complexes are similar to those of tropolone, e.g., tetrakisthiotropone-
thorium(IV) is formed ; however, bisisopropyltropolonenickel(n)is associated
and paramagnetic in solution, whilst the thiotropone analogue is diamag-
netic.lg Anomalies in the intensities of neodymium and erbium triethylene-
tetraminehexa-acetate complexes have been explained.20
The Actinides.-The chemistry of protactinium has been reviewed.21
Radiochemically pure 239Np has been isolated 22 by reversed-phase chroma-
tography. Neptunium(@ oxide is the only product formed 23 on heating
NpO, in vaeuo. Attempts to oxidise americium(m) with perxenate in basic
solution led instead 24 t o the isolation of the complex species
Am,(Xe0,)3,40H,0. If the solution is acidified, americium-(v) and -(vI)
are formed.
The quadrivalent fluorides, LiMF, (M = Np, Pu, Am, Cm), have been
prepared 25 by reduction of the quinquevalent species. The complex halides,
Et,NMX (M = Th or Pa, X = C1 or Br), have been characterised 26 to-
gether with protactinium(Iv) chloride and bromide. Detailed studies of the
electronic spectra and magnetism of uranium(rv) hexahalide complexes,
and phosphine oxide complexes of UC1, and UBr, have appeared.27 Thor-
ium(rv) forms eight-co-ordinated urea complexes,28whilst tropolone and
y-isopropyltropolone form ten-co-ordinated species.29
l4 V. Gutmann, 0. Leitmann, and R. Schutz, Inorg. Nuclear Chem. Letters, 1966,

2, 133.
l5 K. S. Mazdiyasni, C. T. Lynch, and J. S . Smith, Inorg. Chem., 1966, 5, 342.
l* A. F. Ried and P. C . Wailes, Inorg. Chem., 1966, 5, 1213; F. Calderazzo, R.
Pappalardo, and S. Losi, J . Inorg. Nuclear Chem., 1966, 28, 987.
l7 S. J. Lippard, J . Amer. Chem. SOC., 1966, 88, 4300.
la N. I. Lobanov and V. A. Smirnova, Rws. J . Inorg. Chem., 1965, 10, 868; E. V.
Melent’eva, L. I. Kononenko, and N. S. Poluetov, ibid., 1966, 11, 200; S. Herzog and
K. Gustav, 2.anorg. Chem., 1966, 346, 150; S. P. Sinha, J . Inorg. Nuclear Chem., 1966,
28, 189.
l9 E. L. Meutterties, H. Roesky, and C. M. Wright, J . Amer. Chem. SOC., 1966, 88,
4856.
2 o E. A. Bourdreaux and A. K. Mukherji, Inorg. Chem., 1966, 5, 1280.
21 C. Keller, Angew. Chem., Internat. Edn., 1966, 5, 23.
2 2 S. Lis, E. J. Jozefowicz, and S . Siekierski, J. Inorg. Nuclear Chem.. 1966, 28,
199.
23 R. J. Ackerman, R. L. Faircloth, E. G. Rauh, and R. J. Thorn, J . Inorg. NucEear
Chem., 1966, 28, 111.
2 4 Y . Marcus and D. Cohen, Inorg. Chem., 1966,5, 1740.
2 5 T. J. Keenan, Inorg. Nuclear Chem. Letters, 1966, 2, 153.
2 6 D. Brown, J . Chem. SOC. ( A ) ,1966, 766; D. Brown and P. J. Jones, Chern.Comm.,
1966, 279.
2 7 J. P. Day and L. M. Venanzi, J . Chem. SOC. ( A ) ,1966, 197.
2 8 P. S. Gentile, L. S. Campisi, and P. Carfagno, J . Inorg. Nuclear C h . ,1966,
28, 1143.
E. L. Meutterties, J . A m . Chem. SOC., 1966, 88, 305.
G
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The first neptunium(v) compounds to be prepared which do not contain

the Np02+ ion are 30 MINpFs (MI = Na, K, Rb, Cs, NH,) and RbPpF,.
Subsequently, M1,Np0C1, (MI = Cs, Ph,As), Cs,Np0,C13, and CsapO,Cl,
were reported.31 Species MI,PaF, (MI = K, Rb, Cs, NH,) and MI,PaF,
(MI = Li, Na, K, Cs) have been de~cribed.~2 A series of Papers 33 dealing
with protactinium(v) describe the preparation of the pentachloride and
pentabromide; PaOCJ, and PaOBr, are also formed, but in addition some
Pa20Cl, is produced. The latter decomposes in vacuo to Pa,03C1,, then to
Pa02C1. Protactinium(v) chloride forms mono-adducts with the phosphine
oxides R3P0 (R = Ph or m e , ) . The nitrate complexes M1Pa(N03),
(MI = Cs, NhIe,, or NEt,) were prepared from the corresponding chlorides;
more complex species result if the chlorides react with various oxides of
nitrogen.
The uranyl triperoxide ion in Na4U02(0,),,9H,0 has been shown 34 to
have a structure in which the three peroxide groups lie in a plane, with all
six oxygens co-ordinated to the uranium. Compounds MIUP, and Mr,UF',
(MI = Na or K) have been ~haracterised.~5 It is claimed 36 that uraniurn-
(IV) and - (VI)triphenylphosphine complexes previously reported cannot be
prepared, and that the species isolated are, in fact, uranyl-phosphine oxides,
UO2C1,(Ph3PO),. Reduction of UO,Cl, in cyclohexanol in the presence of
triphenylphosphine yields a clathrate, UC1,(Ph3P),,C6Hl1OH.
Titanium, Zirconium, and Habium.-A method for the separation of
zirconium and hafnium, based on the distribution of their thiocyanates
between water and methyl isobutyl ketone, has been proposed.37 A solution
of zirconium tetrabromide in tetrahydrofuran precipitates ZrBr,(diars),
immediately on addition of o-phenylenebisdimethylarsine(diars),38 whilst
the hafnium compound forms only slowly, offering an alternative separation.
The compounds formed are isostructural with TiCl,( diars),. Under aimilar
conditions, TiF, forms (TiF,),diars, and TiI, yields TiI,(diars),, which is not
isomorphous with the chloride.
The preparation of two cyclo-octatetraene (cot) complexes, Ti(cot)
and Ti,(cot), from Ti(OC,N,), has been reported. The structure of the
dimer shows that one cot ring lies between the titaniums, with Ti-C
" bond " lengths ranging from 2-29 to 2.57 A; only the non-bridging rings
30 L. B. Asprey, T. K. Keenan, R. A. Penneman, and G. D. Sturgeon, Inorg.

Nudear Chem. Letters, 1966, 2, 19; L. B. Asprey, F. H. Kruse, A. Rosenweig, and R. A.
Penneman, Inorg. Chem., 1966, 5, 659.
31 K. W. Bagnall and J. B. Laidler, J . Chern. Soc. ( A ) ,1966, 516.
32 D. Brown and J. F. Easey, J . Chem. SOC.( A ) , 1966, 254; M. N. Bucklish, J.
Flegenheimer, F. M. Hall, A. G. Meddock, and C. Ferreira de Miranda, J . Inorg. Nuclear
Chem., 1966, 28, 421.
33 D. Brown, J. F. Easey, and J. G. H. du Preez, J. Chem. Xoc. (A), 1966, 258;
D. Brown a,nd P. J. Jones, ibid., pp. 262, 733, and 874.
3 4 N. W. Alcock, Chem. Comrn., 1966, 536.
35 J. G. Malm, H. Selig, and S. Siegel, Inorg. Chem., 1966, 5, 130.
s s B . W. Fitzsimmons, P. Gans, B. Hayton, and B. C. Smith, J . Inorg. Nuclear
Chem., 1966, 28, 915.
37 W. Fischer, B. Deierling, H. Heitsch, G. Otto, H.-P.Pohlmann, andK. Reinhardt,
Angew. Chem., Internat. Edn., 1966, 5, 15.
38 R. J. H. Clark, W. Errington, J. Lewis, and R. S. Nyholm, J . Chem. SOC.( A ) ,
1966, 989.
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M A B B S -4ND M A C E X N : T E E TRANSITION ELEMENTS 189
are planar.39 Titanium and zirconium diborides have been synthesised,**
as well as two hafnium sulphides,41 WS and Hf,S.
The electronic spectra of a-TiC1, and Cs,Ti,Cl, have been re-interpreted,dz
the higher energy band being attributed to a chasge-transfer process.

Calculations have been performed to obtain energy-level diagrams for ions
[MF,Is- (M = Ti, V, Cr, Fe, C o p 3 Thermodynamic and electrochemical
studies of zirconium-(m) and -(n)chlorides in molten Na-KC1 have been
described.44 The first hexachlorotitanate(rn) complex, (pyH),TiCl,, has
been described,45 as well as Et4NTiCl4,2MeCNand Et4NTiC1,Br,2MeCN.
The adduct (Me,N),TiBr, has been shown 46 to have a trigonal-bipyramidal
structure, and the structure of p-ZrC1, has also been elucidated.47 When
dicyclopentadienyltitanium dichloride reacts with dialkyl or diary1 sulphides,
the product is either cp,TiCl(SR) 48 or C ~ ~ T ~ ( S RThe ) , . former
~~ authors
only obtained the disubstituted species by reaction of cp2TiC1, and the
sodium salt of the corresponding thiol (cp = cyclopentadiene). The inter-
mediate, (cp,TiH),, in the Vol'pin and Shur nitrogen fixation process has
been studied.50
The hexafluorohafnate(rv)ion has been prepared 51 as the hydrazinium
salt; (N2H6),Hf2FI4 has also been obtained. The alkali metal salts M1,ZrC1,
are precipitated 5 2 from a solution of ZrOC1, and MIC1. The far-infrared
spectra of titanium and vanadium tetrachlorides have been assigned,53and
used to calculate thermodynamic data for gaseous VCl,. The heats of
reaction of a number of titanium, vanadium, and chromium tetra-alkoxides
have been reported. 54 Complexes of hexamethylcyclotriphosphazene with
titanium and tin tetrachlorides have been prepared, their formulation
being s5 (Me,PN),MCl,. Although o-phenylenebisdimethylarsineforms eight-
co-ordinate adducts with titanium(IT), the corresponding diethylarsine or
phosphine only form six-co-ordinatecomplexes,whilst the dimethylphosphine
yields eight-co-ordinate species. It is concluded 56 that steric factors are
responsible for the differences. A number of bidentate sulphur ligands only
form 1 : 1 adducts with the chlorides MC1, (3%= Ti, V, Sn),57 whilst the
triarsines bis-(o-dimethylarsinopheny1)methylarsine and tris-1,l,1-(dimethyl-
3s H. Breil and G. Wilka, Angew. Chern., Internat. Edn., 1966, 5, 898.
40 L. Barton and D. Nicholls, J . Inorg. Nuclear Chem., 1966, 28, 1367.
41 H. F. Franzen and J. Graham, J . Inorg. Nuclear Chem., 1966, 28, 377.
4 2 C. Dijkgraaf, J. P. C. van Heel, and J. P. G. Rousseau, Nature, 1966, 211, 185.
4 3 R. F. Fenske, K. G. Caulton, D. D. Radtke, and C. C. Sweeney, Inorg. Chem.,
1966, 5, 960.
4 4 B. Swaroop and S. N. Flengas, Canad. J. Chem., 1966, 44, 199.
4 6 B. T. Russ and G. W. A. Fowles, Chem. Comm., 1566, 19.
4 6 B. J. Russ and J. S. Wood, Chem. Comm., 1966, 745.
4 7 J. A. Watts, Inorg. Chem., 1966, 5, 281.
4 8 R. S. P. Coutts, J. R. Surtees, J. M. Swan, and P. C. Wailes, AusfraE.J . Chem.,
1966,19, 1377.
4 9 H. Kopf and M. Schmidt, 2. anorg. Chem., 1965, 340, 139.
5 0 H. Brintzinger, J . Amer. Chem. SOC.,1966, 88, 4305, 4307.
51 J. Slivnik, B. Jerkovic, and B. Sedej, Monatsh., 1966, 9'7, 820.
5 2 G. M. Toptygina and I. B. Barskaya, Russ. J . Inorg. Chem., 1965, 10, 1226.
63 J. A. Creighton, J. H. S. Green, and W. Kynaston, J . Chem. SOC. ( A ) ,1966, 208.
5 4 D. C. Bradley and M. J. Hillyer, Trans. Paraday SOC., 1966, 62, 2367.
6 5 M.F. Lappert and G. Srivastava, J . Chem. SOC. ( A ) ,1966, 210.
66 R. J. H. Clark, R. H. U. Negrotti, and R. S. Nyholm, Chem. Comm., 1966, 486.
5 7 R. J. H. Clark and W. Errington, Inorg. Chem., 1986, 5, 650.
View Article Online
arsinomethy1)ethaneform 5 8 seven-co-ordinateadducts with TiC1, and VC1,.

A number of mixed n-cyclopentadienyl-maleonitrile-dithiolatecomplexes of
these elements have been rep0rted.~9
The structure of dichlorodiphenoxytitaniurn(rv) is a five-co-ordinate

dimer, involving phenoxy bridging groups.6O The structures of zirconium
and hafnium borohydrides have been deduced 61 from llB n.m.r. studies.
Details of the structure of Ti(NO,), have now appeared.62 The infrared
spectra of a large number of oxo-cations have been investigated;63 it is
suggested that the range of frequencies expected for the metal-oxygen
vibrations is too narrow.
Vanadium, Niobium, and Tantalum.-The metal-cluster compounds of
this group have received some attention this year. A @-formof Nb,Br8 has
been prepared 6 4 by heating the pentabromide and niobium metal; an iodide
can be made similarly. The triangular arrangement of the metal atoms is
retained, the Nb-Nb distance being 2 . 8 8 8 . It is claimed that Nb6IIl is
the f i s t M6x8ion to be prepared for a Group V element; it is formulated as
[Nb618]13,based 6 5 on X-ray evidence. A range of mixed metal compounds
[(Nb/Ta),Br,,]Br,,8H20 have been prepared,66 and it has been shown that
the ion ~b6C11,] 2+ is readily oxidised to [Nb6Cl1,]4+;the salt Nb6Cllp,3EfOH
being isolated. Similarly, [Ta6C1,J2+ may be oxidised by ferric ion to
[Ta6C1,,]4+ ; the intermediate tripositive ion is stable in this system, the
oxidation proceeding by two one-electron steps.67 The far-infrared spectra
of compounds M6X14and M6Xl4,8H2O(M = Nb, Ta; X = C1, Br) have
been analysed.68 The crystal structure 69 of Ta6C114,7H,0 shows that the
six tantalum atoms form a tetragonally elongated octahedron. It is
claimed 7O that speciespreviously formulated as Ta,C1,,,7H20, HTa3C1,,4H,0,
or Ta3C1,0,3H,0 are all Ta,Cl1,,8H20.
Vanadium(m) acetate and benzoate have been prepared from vanadium
diboride; a dimeric structure is proposed 7 1 with four bridging and two
terminal carboxylate groups. Trigonal prismatic co-ordination of a first-
row transition element has been established 7 2 in the tris-dithiolato-com-
pound V(S,C2Ph&. The very similar, (3.05-3.1 1 A), sulphur-sulphur
distances in the rhenium, molybdenum, and vanadium compounds suggest
that S-S interactions determine the type of structure formed. Complexes
68 R. J. H. Clark, M. L. Greedeld, and R. S. Nyholm, J. Chem. SOC.( A ) , 1966,
1254.
59J. Locke and J. A. McCleverty, Inorg. Chem., 1966, 5, 1157.
6oK. Watenpaugh and C. N. Caughlan, Inorg. Chem., 1966, 5, 1782.
B. D. James, R. K. Nanda, and M. G. H. Wallbridge,J . Chem. SOC.( A ) ,1966,183.
6 2 C. D. Garner and S. C. Wallwork, J . Chem. SOC. ( A ) ,1966, 1496.
63 J. Selbin, Angew. Chem., Internat. Edn., 1966, 5, 712.
6 4 A. Simon and H. G. von Schnering, J . Less-Common Metds, 1966,11, 31.
6 5 L. R. Bateman, J. F. Blount, and L. F. Dahl, J . Amer. Chem. SOC.,1966, 88,
1082.
6 6 H. Schiifer and B. Speckelmeyer, J . Less-CommonMetals, 1966, 11, 73.
6 7 J. H. Esponson and R. E. McCarley, J . Amer. Chem. SOC., 1966, 88, 1063.
8 8 P. M. Boorman and B. P. Straughan, J . Chem. SOC. ( A ) ,1966, 1514.
6 9 R. D. Burbank, Inorg. Chem., 1966, 5, 1491.
7 0 H. Schlifer and D. Bauer, 2. anorg. Chem., 1965,340, 62.
7 1 N. N. Greenwood, R. V. Parish, and P . Thornton, J . Chem. SOC. ( A ) , 1966, 320.
7 2 R. Eisenberg, E. I. Stiefel, R, C. Rosenberg, and H. B. Gray, J . A m r . Chem.
SOC.,1966, 88, 2874.
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MABBS A N D MACHIN: THE TRANSITION ELEMENTS 191
R+[VX4,2CH,CN](R+ = Et,N, MePh,As, or Ph,As; X = C1,Br) have been
prepared from VX3,3MeCN. The tetraethylammonium salt forms complexes
Et,N[VCl,,ZL] ligand L = pyridine, 8 2,2'-bipyridyl, or Q 1,lO-phenanthro-
line) by direct reaction, and desolvates a t 100"c to form a tetrahedral

species, Et,NVCl,.
Niobium tetrahalides slowly form 1 : 1 adducts with triethylamine, but
only the chloride reacts completely ;74 the products are diamagnetic and
presumed to retain a dimeric structure. Several diamines also formed
1 : 1 complexes. The e.8.r. spectrum of vanadium tetra-t-butoxide shows
unexpectedly low g-~alues.7~ Several new vanadyl chloro-complexes have
been prepared and characterised;76 they are formulated as M1,VOCl,,xH,O.
Five-co-ordinated structures are suggested 7' for a number of vanadyl-Schiff
base complexes. Extended Huckel calculations on the vanadyl-porpkin
system have been published; energies for all of the d-d transitions are
calculated.78 Thermochemical data for pervanadyl (VO,+) and vanadyl
(VOZ+) ions in solution are a ~ a i l a b l e . ~ ~
The ions [TaF,]- and [TaF7]2- have been identified in a study of the
Raman spectra of the system Ta(v)-HF-NH,F-H,O ; the octafluoro-ion
was not detected in solution. Fluorotetrachlorotantalum(v) is a tetramer 81
formed by bridging fluorine ions. A number of oxychloride compoundsy
e.g., VOC1, and POCl,, can be made 8 2 by reaction of aluminium chloride
with the oxide or an oxyion in molten Li-Na-KC1; TaOCl, is formed s3
when TaCl, or M'TaCl, react with Sb20,. Assignments of the metal-oxygen
and metal-halogen frequencies have been made 84 for the infrared spectra
of compounds M1,[MvOX5](MI= Rb, Cs; Mv = Nb, Mo, or W; X = C1, Br).
Infrared and Raman studies s5 of vanadate(v) solutions at various pH values
have also been described, and assignments proposed for the ions V0,3-,
HV04,-, v2074-y HV,0,3-, and (V03)1,n-. The molecular structure of the
isopolyvanadate ion (V10028)6-, in K2Zn,Vlo0,8,16H,0, has been deter-
mined.86 Amperometric studies 87 of thorium polyvanadates have estab-
lished the pH ranges in which the ortho-(3Th0,2V2O,),meta-(Th0,ZV,05),
and pyro-(ThO,V,O,) species are stable.
Chromium, Molybdenum, and Tungsten.-Reactions of the zero-valent
cyanide complexes K,Cr(CN), and K,Ni( CN), with phosphorus-, arsenic-,
and nitrogen-donorsin liquid ammonia have been studied;88complete ligand
7s R. J. H. Clark, R. S. Nyholm, and D. E. Scaife, J . C h m . SOC.( A ) , 1966, 1296.
'* T. M. Brown and G. S. Newton, Inorg. Chem., 1966, 5, 1117.
7 6 G. F. Kokoszka, H. C. Allen, and G. Gordon, Inorg. Chem., 1966, 5 , 9 1 .
7 6 P. A. Kilty and D. Nicholls, J . Chem. SOC.( A ) ,1966, 1175.
7 7 L. Sacconi and U. Canipigli, Inorg. Chem., 1966, 5, 606.
M. Zerner and M. Gouterman, Inorg. Chem., 1966, 5, 1699.
7 9 G. L. Bertrand, G. W. Stapleton, C. A. Wulff, and L. G. Hepler, Inorg. Chem.,
1966, 5, 1283.
0. L. Keller and A. Chetliam-Strode, Inorg. Chem., 1966, 5, 367.
H. Preiss, 2. anorg. Chem., 1966, 346, 272.
R. S. Drago and K. W. Whitten, Inorg. Chem., 1966, 5, 677.
83 I. S. Morozov and A. I. Rlorozov, Rzlss. J . Inorg. Chem., 1966, 11, 182.
8 4 A. Sabatini and I. Bertini, Inorg. Chem., 1966, 5, 204.
W. P. Griffith and T. D. Wickins, J . Chem. SOC.( A ) ,1966, 1087.
8 6 H. T. Evans, Inorg. Cliem., 1966, 5 , 967.
8 7 R. S. Saxena and 0. P. Sharma, J . Inorg. Nudear Chem., 1966, 28, 195.
H. Behrens and A. Muller, 2. anorg. Chem., 1965, 341, 124.
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replacement occurs in the chromium case for bi- and ter-dentate ligands, but
the reactions proceed best with uni- or bi-dentate ligands in the nickel case.
The e.s.r. spectra of the nitrosyl complexes [Cr(CN),N0]3-, [CrNO(NH,),] 2+,
and [CrNO(H,O),] 2+ have been interpreted,89 and molecular orbital calcula-

tions made for the energy levels of the pentacyanonitrosyl complex.90
salts of the metal-cluster [W6Br816+have been is01ated;~lthe cluster
may be reduced with bromide ion to [W6Br814+.An incomplete description
of the preparation of a tungsten dihydride has appeared.92 A peroxy-
bridged chromium compound, (H20),Cr-O-O-Cr( H,O),, has been isolated 93
from the reaction products of chromic acid and hydrogen peroxide. The
magnetic properties of KCrF,, Na,CrF,, chromium(11) 2,2’-bipyridyl and
o-phenanthroline complexes, and a series of chromium(rr)double sulphates
have been studied.g4 The magnetic and spectral properties of the methoxide
compounds M(OMe), (M = Cr, Mn, Fe, Co, Ni, Cu) and M’(OMe), (M’ = Ti,
Cr, Fe) have also been inter~reted.~5The chromium(n) and copper@)
species are said t o be antiferromagnetic. Five-co-ordinated compounds have
been reported with 96 diethyldithiocarbamate (MI1 = Cr, Mn, Fe, Zn) and
tris-(2-dimethylaminoethyl)amine(MI1 = Cr--Zn). The chromium(rr)com-
plexes with dimethyl sulphoxide (DMSO), CrX2,2DMS0 (X Cl, Br, I), =1
are said to have distorted octahedral structures; the corresponding aceto-

nitrile complexes are also octahedral polymers.97 Molybdenum phthalo-
cyanine has been prepared 98 for the first time, and its infrared spectrum
studied.
A convenient method for the preparation of chromium, molybdenum,
and tungsten tri-iodides is by reaction of iodine with the corresponding
hexacarbonyl~.~~ Chromium(=) methoxide results 100 when tricarbonylarene-
chromium compounds are photochemically decarboxylated in methanol. A
comprehensive study of methionine complexes of Ag(I), Mh, Co, Ni, Cu, Zn,
Cd, Hg, and Pb(n), and Cr, Fe, Al,Bi, and Rh(m) has been reported.lol
The SCH, group is not co-ordinated in these complexes, but can be made to
co-ordinate to a second metal, forming, e.g., [Cr,Ag,(methi~nine),](ClO~)~.
With silver(I), the sulphur first co-ordinates; the -NH2 and -C02- can then
L. S. Meriwether, S. D. Robinson, and G. W i k s o n , J . Chem. SOC.( A ) , 1966,
1488.
go P. T. Manoharan and H. B. Gray, Inorg. Chem., 1966, 5, 823.
9l H. Schlifer and R. Siepmann, J . Less-Common Metals, 1966, 11, 76.
Sa E. F. Speranskaya and T. G. Pokhvalitova, Russ. J . Inorg. Chem., 1965, 10,
1303.
Q3 M. Ardon and B. Bleicher, J . Amer. Chem. SOC., 1966, 88, 858.
94 A. Earnshaw, L. F. Larkworthy, K. C. Patel, K. S. Patel, R. L. Carlin, and E. G.
Terezakis, J . Chem. SOC.( A ) , 1966, 511; A. Earnshaw, L. F. Larkworthy, and K. S.
Patel, ibid., p. 363; A. Earnshaw, L. F. Larkworthy, and K. C. Patel, Chem. Comm.,
1966, 181.
Q 5 R. W. Adams, E. Bishop, R. L. Martin, and 0. Winter, Austral. J. Chem., 1966,
19, 207.
s 6 J. P . Fackler and D. G. Holah, Inorg. Nuclear Chem. Letters, 1966, 2, 251; M.
Ciampolini, Chem. Comm., 1966, 47.
9’ D. C. Holah and J. P . Fackler, Inorg. Chern., 1965, 4, 1721; 1966, 5, 479.
O8 F. H. Shurvell and L. Pinzuti, Cunad. J . Chem., 1966, 44, 125.
9s C. DjordjeviE, R. S. Nyholm, C. S. Pande, rand M. H. B. Stiddard, J . ChemSoc.
( A ) ,1966, 16.
100 D. A. Brown, D. Cunningham, and W. K . Glass, Chem. Comm., 1966, 306.
lo1 C. A. McAuliffe, J. V. Quegliano, and L. M. Vallarino, Inorg. Chem., 1966,5,1996.
View Article Online
M A B B S A N D MACHIN: THE TRANSITION E L E M E N T S 193
be bonded to nickel or copper(n). The spectrum of hexa-imidazolidone-
chromium(m) has been shown to be identical with that of the hexa-urea
complex, whilst in the trisbiuret complex the spin-allowed d d bands are
shifted.lo2 It is thought that CrCI,,ZNMe, is five-co-ordinated loalike the

titanium and vanadium analogues. Acetonitrile complexes [MoCl,,MeCN] 2-
and [MoC13,3MeCN]MeCN have been characterised.lo4 The tris- (cis-stilbene-
dithio1ato)M complexes (M = Mo, W, Re) are trigonal prisms. Tris(to1uene-
3,4-dithiolato)- and benzene-l,2-dithiolato-complexes are also reported for
these metals.105 Two other extensive Papers have appeared l o 6 dealing
with dithiolato-complexes of chromium, molybdenum, and tungsten.
A review of the oxo-compounds of molybdenum-(v) and -(vI) has
appeared.lo7 When MOB, reacts with, e.g., PCl,, CCI,, or SiCI,, one of the
products is Mo,Cl,F,; evidence that this is [Mo,C~,]~+[MOF,],+ is pre-
sented.lo8 I n methanol solution, molybdenum(v) chloride forms logtruns-
[(MeO),MoCl,]-; the e.s.r. and electronic spectra of the pyridinium salt have
been studied. I n thionyl chloride, molybdenum, tungsten, and rhenium
form the oxytetrachlorides, whereas most metals form their chlorides.
The reaction mixture W +
WO, +
I, yields W021, when heated in a sealed
tube;lll WOC1, has also been studied.112 The infrared and mass spectra of
compounds Mo0,X2 and WO,X, (X = C1, Br) have been recorded, some of
the infrared work being on gaseous ~amples.1~3 The co-ordination chemistry
of MoO,Cl, and MoOC1, has also received attention.l14 The e.s.r. spectra
of the octacyano-molybdate and -tungstate(v) ions in frozen glycerine are
consistent 115 with Archimedean antiprismatic structures, but the solid
potassium salts appear to be dodecahedral.
High pressure (65 kbars) syntheses 116 of alkali-metal molybdenum
bronzes have been described. The coprecipitation of anatase with molyb-
denum- or tungsten-trioxide enhances their sensitivity to photoreduction,l17
although no new compounds are formed. A series of heteropolyelectrolytes
[ ~ ~ ~ m ~ ~ 6 ~ Z f ~ 4 ~ 1 1 ~ 3 has been
0 ] ~ 1 ~ synthesised.llg
- ~ - ~ - ~ ~ - The cubic
phases shrink reversibly when dehydrated or heated; e.g., the cell edge of
lo2 K. K. Cha,tterjeeand G. B. Porter, Inorg. Chem., 1966, 5, 860.

l o 3G. W. A. Fowles and P. T. Greene, Chem. Comm., 1966, 784.
1 ° 4 P. W. Smith and A. G. Wedd, J . Chem. SOC. ( A ) , 1966, 231.
l o 5E. I. Stiefel, R. Eisenberg, R. C. Rosenberg, and H. B. Gray, J . Amer. Chem.
SOC., 1966, 88, 2956.
lo6G. N. Schrauzer and V. P. Mayweg, J . Amer. Chem. SOC.,1966, 88, 3236, G. N.
Schrauzer, V. P. Mayweg, and W. Heinrich, ibid., p. 5174.
lo’ P. C. H. Mitchell, Quart. Rev., 1966, 20, 103.
lo*D. F. Stewart and T. A. O’Donnell, Nature, 1966, 210, 836.
l o gD. A. McClung, L. R. Dalton, and C . H. Brubaker, Inorg. Chrn., 1966, 5, 1985.
I 1 O D. A. Edwards and A. A. Woolf, J. Chem. SOC. ( A ) ,1966, 91.
l l 1 J. Tillack and P. Eckerlin, Angew. Chem., Internat. Edn., 1966, 5, 421.
Ira G. W. A. Fowles and J. L. Frost, Chenz. Comrn., 1966, 252.
113 C. G. Barraclough and J. Stals, Austral. J . Chem., 1966, 19, 741; T. V. Iorns
and F. E. Stafford, J . Amer. Chem. SOC.,1966, 88, 4819.
114 M. L. Larson and F. W. Moore, Inorg. Chem., 1966, 5, 801.
115 B. R. McGarvey, Inorg. Chem., 1966, 5, 476.
116 T. A. Bither, J. L. Gilson, and H. S. Young, Inorg. Chem., 1966, 5, 1559.
117 J, A. Chopoorian, G. H. Dorion, and F. S . Model, J . Inorg. Nuclear Chem., 1966,
28, 83.
l 1 * L. C. W. Baker, V. S . Baker, K. Eriks, M. T. Pope, M. Shibata, 0. W. Rollins,
J. H. Fang, and L. L. Koh, J . Amer. Chem. SOC.,1966, 88, 2331.
View Article Online
194 IN 0R GI.AN10 C H E MI S1 R Y
(~4),Na2[Ga06H,04Wl1030],15H20 falls continuously from 22-17A a t 10”
to 21.84 A a t 4 7 ” ~ . Di- and tri-molybdates do not exist llg in aqueous
solution, the tetramolybdate being the first species formed when molybdate
solutions are acidified. The hetero-9-molybdate ions have been shown to be

stable monomers a t high concentrations in solution, but they decompose on
dilution. The pR’s of the unstable acid H,MnMo,O,, have been deter-
mined.120 The alkaline degradation of metatungstate [W1203,(0H),l6- is
birnolecular,l2l with an activation energy of -9.8 kcal. mole-l.
Manganese, Technetium, and Rhenium.-Rhenium(v) chloride is re-
duced by copper in the presence of trifluorophosphineto form Re(PF3),Cl;
Ir(PF3)41is formed by oxidation of KIr(PF,),.
Both tc- and p-forms of manganese titanate are ferrimagnetic as are
the phases Mn1+02+Mz-223+Tic04 (M3+= Ti, V, Cr). Tetrahedral seleno-
cyanate complexes of Mn-Zn(rr), and octahedral Mn,Ni(n), and Fe,Y(m)
complexes are [Rh(seCN)6]3- and [M(SeCN),I2- (M = Pd, Pt)
are selenium-bonded, the remainder being nitrogen-bonded. The cyanide
complexes K4Re(CN),,3H,O and Na4Re(CN),,5H,0 are both reported 126 to
be diamagnetic. Various complexes of the bivalent ions Mn-Zn have been
prepared with pyridine, y-picoline, quinoline, 2,2’-diaminobiphenyl, and
pentamethylenetetrazine.126 The far-infrared spectra l27 of many y-picoline
and thiourea complexes have been assigned. The 2,2’,2”-terpyridyl com-
plexes of manganese, cobalt, and copper(n), (MLCl,), are isomorphous 128
with the zinc analogue and are thus five-co-ordinated; the quadridentate
ligand tris- (2-dimethylaminoethy1)amineforms complexes which are formu-
lated as [MLXIX [M = M, Fe, Zn(n); X = halogen], and the terdentnte
ligand bis-(2-dimethylaminoethyl)methylamine also forms five-co-ordinated
complexes, [MLX,].129
No new meta.1-cluster compounds have been reported for these metals;
however, a number of structural determinations have appeared, and some
reactions of known specie8 studied. The structures of (Ph,As),[Re3Clll] and
Cs2[Re,Brll] are based l 3 0 on that of Re3Cl12, but one terminal, in-plane
halogen atom is absent. Metal-metal bond lengths to the unique rhenium are
shorter than the remaining bond (2.43 cf. 2.49, and 2.44 cf. 2-48A in the
0.
l L g Glemser and W. Holtje, Angew. Chem., Internat. Edn., 1966, 5 , 736.
lZo L. C. W.
Baker and T. J. R. Weakley, J . Inorg. Nuclear Chem., 1966, 28, 447.
121 0.Glemser, W.Holznagel, and W. Holtje, 2. anorg. Chem., 1966, 342, 75.
1 2 2 T.Kruck, A. Englemann, and W. Lang, Chern. Ber., 1966,99, 2473.
lZ3 P. Hagenmuller, Ch. Guillaud, A. Lecerf, M. Rault, and G. Villers, BulZ. SOC.
chim France, 1966, 2589.
1 2 4 J. L. Burmeister and L. E. Williams, Inorg. Chem., 1966, 5, 1113; D. Forster
and D. M. L. Goodgame, ibid., 1965, 4, 1712.
lZ6 S. Sen, 2. anorg. Chem., 1965, 340, 82.
lZ6 D.H. Brown, R. H. Nuttall, J. McAvoy, and D. W. A. Sharp, J . Chem. SOC.( A ) ,
1966, 892; F. Hein and W. Jehn, 2. anorg. Chem., 1965,341,244;F.M.D’Itri and A. I.
Popov, Inorg. Chem., 1966, 5, 1670.
12’ M. Goodgame and P. J. Hayward, J . Chem. SOC. ( A ) ,1966, 632; C. D. Flint and
M. Goodgame, ibid., p. 744.
12* C. M. Harris, T. N. Lockyer, and N. C . Stephenson, Austral. J . Chem., 1966,
19, 1741.
1 2 9 M. Ciampolini and G. P. Speroni, Inorg. Chem., 1966, 5 , 45; M. Ciampohi and
N. Nardi, ibid., p. 1150.
130 B. R. Penfold and W. T. Robinson, I w g . Chem., 1966, 5, 1758; M. Elder and
B. R . Penfold, ibid., p. 1763.
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MABBS AND MACHIN: THE TRANSITION ELEMENTS 195
chloride and bromide, respectively). The structure of Re3Br,(AsO,),,3DMSO
also retains the triangle of rhenium atoms ;I31 three oxygens of the arsenate
are bonded to the triangle of rheniums, one above and one below the plane.
Reactions 132 of the [Re,X,I2- ion yield ReX,(Ph,P),, [Re(diphosphine)Cl,],

carboxylates Re,(O,CR),X,, and 2,5-dithiahexane forms Re,Cl,L,. The
structure of the last complex is a dimer [ReCl,][ReL,Cl]; the ReC1, and
ReS, planes are not eclipsed, and thus not &bonded. Molten dimethyl
sulphone does not react 133 with Re,Cl,, but addition of chloride ion yields
[Re,C1,I2-. I n fused Li-KC1 eutectic, this reaction yields rhenium(0) and
[ReCl,] ,-. Re,Cl, reacts 134 with 2,2'-bipyridyl, o-phenanthroline, diphos-
phines, and 2,5-dithiahexane, t o yield complexes Re,Cl,L,., for all except
the o-phenanthroline; their spectra suggest that the trimeric structure is
retained in the adducts. Re3C1,L, species are formed with unidentate
ligands, L.
The trigonal prismatic co-ordination of tris-(cis-lY2-diphenylethane-l ,2-
dithio1ato)rhenium has been confirmed.135 Other trismaleonitriledithiolate
complexes of manganese, iron, molybdenum, and tungsten are suggested as
having this structure.
The spectra of tris-dithiocarbamate, 2,2'-bipyridyl, and acetylacetonato-
complexes of manganese(m) have been assigned.13' The 5Bg+ 5T2g
transition occurs at N 20,000 cm.-l, t.he lower energy (5000--15,000 cm.-l)
band being attributed to a charge-transfer process. Pentachloromangan-
ate(=) complexes are formed 138 when concentrated hydrochloric acid
reacts with potassium pernianganate in the presence of, e.g., 2,2'-bipyridyl ;
a t lower acidity, MnLCl,,H,O is formed, as well as MnLCl,. The thermal
decomposition of pyridine (py) adducts ReBr3,2pyand [ReO,py,]Br has been
r e ~ 0 r t e d . l The
~ ~ spectra of K,ReCl, in molten dimethyl sulphone, diethyl-
amine hydrochloride, or Li-KC1 eutectic reveal a, larger splitting l 4 0 of the
ligand-field bands in the latter solvent. Crystals of technetium(Iv) chloride
contain zig-zag chains of octahedra sharing two edges.141 This compound
forms 142 octahedral adducts TcC14L2(L = Ph,P or Ph3As),TcCl,bipyridyl,
and [TcCl,(bipyridyl),]Cl,. Bisdiphenylphosphinoethaneforms the tervalent
complex [TcCl, (diphos)JC1.
The physical properties of compounds MITcF, (MI= Na, K, Rb, Cs)
have been studied.la3 A square-pyramidal structure is proposed 14, for
131 F. A. Cotton and S. J. Lippard, J. Amer. Chem. SOC.,1986, 88, 1882.
132 F. A. Cotton, N. F. Curtis, and W. R. Robinson, Inorg. Chem., 1935, 4, 1696;
F. A. Cotton, C. Oldham, and W. R. Robinson, ibid., 1966, 5, 1798; M. J. Bennett,
F. A. Cotton, and R. A. Walton, J. Amer. Chem. SOC.,1906, 88, 3866.
133 R. A. Bailey and J. A. McIntyre, Inorg. Chem., 1966, 5, 1940.
134 F. A. Cotton and R. A. Walton, Inorg. Chem., 1966, 5 , 1802.
135 R. Eisenberg and J. A. Ibers, Inorg. Chem., 1966, 5, 411.
136 M. Gerloch, S. F. A. Kettle, J. Locke, and J. A. McCleverty, Chem. Comm.,
1966, 29.
13' R . Dingle, Acta Chem. Scand., 1966, 5, 33.
138 H. A. Goodwin and R. N. Sylva, Austral. J. Chem., 1965, 18, 1743.
13D V. G. Tronev and R. A. Dovlyatskina, Russ. J. Inorg. Chem., 1965, 10, 1230.
140 R. A. Bailey and J. A. McIntyre, Inorg. Chent., 1966, 5, 964.
141 M. Elder and B. R. Penfold, Inorg. Chem., 1966, 5, 1197.
142 J. E. Fergusson and 5. H. Hickford, J. Inorg. Nuctear Chem., 1966, 28, 2293.
143 D. Hugill and R . D. Peacock, J. Chem. SOC. ( A ) ,1966, 1339.
144 F. A. Cotton and S. J. Lippard, Inorg. Chem., 1966, 5, 9.
View Article Online
the [ReX,O]- ion (X = C1, Br, I). K3&O, is stable to at least 800°c,
but K2Mn04decomposes reversibly a t MO-680 OC. The initial decomposi-
tion products on heating KMnO, are K,MnO,, &&O,, and MnO,. I n a
study of the oxidising power of metal hexafl~orides,l~~ it was shown that

ReF6 oxidises nitric oxide, yielding NO+ReF6; with NOE', (NO),ReF, was
formed. The chemistry of rhenium-(Iv) and -(v) oxychlorides has been
investigated.147 In alkaline solutions, B+[ReOCZ,] (B+ = Ph,As, Et,N, or
acridinium) disproportionates to rhenium-(Iv) and -( vr1).14g Rhenium
hydride-phosphine complexes are harder to prepare than those of other
metals; compounds ReH,(PR,),, [ReH,(PR,),],, and ReH5(PR3),have been
is01ated.l~~Barium and strontium nitrides react with rhenium to form l50
the ternary species M,Re,N,, (M = Ba, Sr). Osmium only forms the barium
compound. A thermally unstable compound Sr,,Re5N,, was also detected.
Iron, Ruthenium, and Osmium.-Dinitrosyl iron, cobalt, and nickel
halides react with either tetraphenyldiphosphine or diarsine to give the
following (NO)2Fe(Ph2PPPh2)a, [(NO),Fe(Ph,PPPh,)J,, [X(NO),BeEPh,],,
[(NO),FeEPh,],, [X(NO),CoPh,EEPh,Co( NO),X],, [(Ph,PPPh,) (NO)NiX),,
and [X(NO)NiAsPh,], (E = P or As; X = halide).151 With iron and cobalt
nitrosylcarbonyls and 1,2-bis(dipheny1phosphino)ethane ( = diphos) the
compounds [Fe(NO),(diphos)], [Co(NO)(CO)(diphos)],
[&(NO)(C0),l2( diphos), and [(NO),(CO)Fe(diphos)Co(NO)(CO),] were
isolated.l 5 2
The complexes [FeS,C,(CF,),], [FeS,C,Ph,], and [CoS,C,Ph,] have been
reported to be metal-sulphur bridged dimers with structures analogous to
that of [Co,S4C4(CF3),],. Their electronic properties and reactions with
phosphines and Fe(CO), were also given.153 The polarography of
~S,C,(CF,),], (M = Fe or Co) shows the following one-electron reduction
processes:
[MS4C4(CF,)& +[MS-iC,(CFd4]2- * CMS&I(CFJ~I-
The isolation and magnetic properties of the mononegabive dimers, and
of similar rnaleonitrile-dithiolate (mnt2-) and toluene-3,4-dithiolate (tdt2-)
compounds were also described.154 Similar polarographic studies indicated
the existence of [M(tdt)J2- and [M(tdt),]- complexes (M = Fe, Co, Ni, Pt,
Cu, Au), but only the [M(tdt),]- (M = Fe, Co, Au) compounds could be
isolated.155 The preparations and magnetic properties of some complexes
145 H. Peters, K. H. Radeka, and L. Till, 2. anorg. C h m . , 1 9 6 6 , 3 4 6 , l .

146 N.Bartlett, S. P. Beaton, and N. K. Jha, Chem. Comm., 1966, 168.
14' G. Rouschias and G . Wilkinson, J. Chern. SOC.( A ) ,1966, 465; D. E. Grove and
G. Wilkinson, &id., p. 1224.
l48 B. J. Brisdon and D. A. Edwards, Chem. Comm., 1966, 278.
140 J. m a t t and R. S . Coffey, Chem. Comm., 1966, 545.
l50 F.K.Patterson and R. Ward, Inorg. Chem., 1966, 5, 1312.
151 W. Hieber and R. Kummer, 2. anorg. Chem., 1966, 344, 292.
152 R. J. Mawby, D. Morris, E. M. Thorsteinson, and F. Basolo, Inorg. Chem., 1966,
5, 27.
153 G.N. Schrauzer. V. P. Mayweg, H. W. Finck, and W. Heinrich, J. Amer. Chem.
1 -
SOC.,1966, 88, 4604.

154 A. R. Balch and R. H. Holm, Chem. Cornm., 1966, 552.
155 R. Williams, E.Billig, J. H. Waters, and H. B. Gray, J. Amer. Chem. SOC., 1966,
88, 43.
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MABBS AND M A C H I N : THE TRANSITION ELEMENTS 197
of the types [Fe(NO)S,C,Ph,] -, [Fe(NO)S,C,Ph,] -, [Fe(NO)S,C,Ph,]o, and
[Fe(NO)S,C,Ph,],- have also been reported.ls6
A series of complexes of the type Fe phen,X, (X = C1, Br, NCS, NCSe,
OCN, N,, HCO,, CH,CO,) have been prepared and shown to be high-spin
with peffin the range 5-1-5.3 B.M.l57 The magnetism and electronic spectra
of the complexes with X = C1, Br, and N3have been interpreted on the basis
of molecular orbital models based on C,, of DPh syrnmetrie~.l5~When
X = NCS or NCSe the magnetic behaviour has been interpreted in terms
of a 5T, + lAl eq~ilibrium.l5~The magnetic susceptibility data over the
temperature range 77-300"~ and the Mossbauer spectral data of the com-
plexes [Fe phen,X]nH,O (X = oxalato, n = 5 ; or X = malonato, n = 7)
have been discussed in terms of a spin-triplet ground state.160 The relation-
ship between peffand the Mossbauer quadrapole splitting parameter, d E Q ,
for the complexes Fe py4X, (X = Cl, Br, I, NCS, OCN) has been discussed
with the assumption that they are tetragonally distorted octahedral com-
plexes.161 The Mossbauer spectra of iron(@ phthalocyaninedipyridine,162
iron-(II) and -(m)substituted salicylaldo~irne,l6~ nucleotide, nucleic acids,
and EDTA complexes 164 have been discussed in terms of the modes of
metal-ligand bonding. Similar Mossbauer spectral studies coupled with
infrared and electronic spectra have been used to distinguish [FeCl,]- from
[FeC1,I3- ions,165 and to discuss the structures of Fe phen,X, and
[Fephen,]X, (X = Cl, Br, NCS, OCN, HC0,).166
The changes, due to pressure, in the electronic absorption spectrum of
Gillespite, BaFeSi,O,,, have been interpreted in terms of changes in metal-
ligand distances causing spin-pairing.167 The absorption spectra of the
complexes [M bipy3]Br,,6H,0, [M bipy3]S0,,7H20 ( M = Fe, Ru, Co, Ni,
Cu), [FeL,X,] (L = isoqinoline, /I- and y-picoline, 4-cyanopyridine, 3,5-
dichloropyridine; X = halide), [M bipy2X2],, [M bipy2X,]X (M = Fe, Ru,
0 s ; X = C1, Br, I),and [Ru(diamine),]X, (X Br, I, SCN, $S203)have been
reported and discussed in terms of deviations from octahedral symmetry,
metal-ligand bonding, and ligand-field parameters.16* Further studies of
the optical spectra of [Fe(CN),NOI2- have led to the suggestion of the
156 J. Locke, J. A. McCleverty, E. J. Wharton, and C. J. Winscorn, Chem. Comm.,

1966, 677.
15' K. Madeja, W. Wilke, and S. Schmidt, 2. anorg. Chem., 1966, 346, 306.
158 P. Spacu and C. Lepadatu, J. Amer. Chem. SOC.,1966, 88, 3221.
159 E. Konig and K. Madeja, Chem. Comm., 1966, 61.
160 E. Konig and K. Madeja, J. Amer. Chem. SOC.,1966, 88, 4528.
1 6 1 R. M. Golding, K. F. Mok, and J. F. Duncan, Inorg. Chem., 1966, 5, 774.
162 A. Hudson and H. J. Whitfield, C h m . Comm., 1966, 606.
163 K. Burger, L. Korecz, I. B. A. Manuaba, and I?. Mag, J. Inorg. Nuclear Chem.,
1966, 28, 1673.
lB4 I. N. Rabinowitz, F. F. Davis, and R. H. Herber, J. Amer. Chem. SOC.,1966,
88, 4346.
G . M. Bancroft, A. G . Maddock, W. K. Ong, and R. H. Prince, J. Chem. SOC.( A ) ,
1966, 723.
166 J. F. Duncan and K. F. Mok, J. Chem. SOC. ( A ) ,1966, 1493.
16' R. G. J. Strens, Chem. Cornm., 1966, 777.
168 D. 35. L. Goodgame, M. Goodgame, M. A. Hitchman, and M. J. Weeks, Inorg.
Chem., 1966, 5, 635; R . A. Palmer and T. S. Piper, ibid., p. 864; J. E. Fergusson and
G. M. Harris, J. Chem. SOC.( A ) , 1966, 1293; H. H. Schmidtke and D. Garthoff, Hdv.
Chim. Acta, 1966, 49, 2039.
View Article Online
following revised energy-level scheme :I69

ZZ,YZ < XY < n*NO < Z ' - y8 < Z'
The infrared spectra of complexes MX2,2NH, (M = Fe, Co, Ni, Cu,Zn,
Cd, Hg, Pd, P t ; X = C1, Br, I) in the range 4000-200 cm.-l have been
reported, and the M-N and M-halogen stretching frequencies discussed in
relation to the structures of the complexes.lV0 I n the complexes
[Ru,(OCOR),Cl] (R = Me, Et, Pr"), which contain ruthenium in the for-
mal oxidation states II and m, the room-temperature magnetic moments
suggest that some of the ruthenium is in the spin-free state.lV1 The magnetic
moments and electronic spectra of a number of iron(=), cobalt(@, nickel(n),
copper(=), and zinc(n) Schiff base and other nitrogen-donor complexes have
been used to suggest their structures.172
The magnetic susceptibility data for several spin-paired iron(m) and
ruthenium(m) complexes,173and the near-infrared spectrum of Os(acac),l74
have been interpreted in terms of a ,TZgground state which has been per-
turbed by spin-orbit coupling and an axial ligand-field component. The
preparation, magnetic properties, and structures of a binuclear and a mono-
nuclear form of [Fe(salen)Cl]have been described.lV6 In the diethyldithio-
carbamate complex, [Fe(S,CNEt,),Cl], magnetic susceptibility measurements
and an X-ray structure determination have shown it to contain five-
co-ordinate (essentially square-pyramidal) iron(@ with a spin quartet
ground-state.lV6 The Mossbauer and proton n.m.r. spectra of several other
iron(m) dithiocarbamate complexes have been interpreted in terms of the
symmetry of the ligand field and iron d-electron delocalisation.177 The
magnetic exchange interactions in trimeric n-alkoxide complexes, [Fe,( OR),],
have been interpreted in terms of a dipolar coupling scheme for a triangular
cluster of spin-free iron(m) ions (8= 5/2),178whilst in the complexes
[Fe,O(phen),]X, (X = C1, NO,) each interacting iron has been assumed to
have a spin-paired ground state (8= +).l79
Magnetic susceptibility, electrical conductivity, and infrared spectral
measurements have been used t o deduce that in the complexes [FeBX,]Y
(X = C1, Br, I, NCS; Y = ClO,, BF,, NCS; B = the quinquedentate
2,13-dimethyl-3,6,9,12,18-penta-azabicyclo[ 12,3,lloctadeca-1( 18),2,12,14,16-
160 H. B. Gray, P. T. Manoharan, J. Pearlman, and R. F. Riley, Chem. Comm.,
1966, 62.
l70 R. J. H. Clark and C. S. William, J . Chem. SOC.( A ) ,1966, 1425.
171 T. A. Stephenson and G. Wilkinson, J . Inorg. Nuclear Chem., 1966, 28, 2285.
172 J. R. Allan, D. H. Brown, R. H. Nuttall, and D. W. A. Sharp, J . Chem. SOC.( A ) ,
1966, 1031; L. F. Lindsay, S. E. Livingstone, T. N. Lockyer, and N. C. Stephenson,
Austral. J . Chem., 1966, 19, 1165; W. R. McClellan and R. E. Benson, J . Amer. Chem.
SOC.,1966, 88, 5165; M. A. Robinson and T. J. Hurley, Inorg. Chem., 1965, 4 , 1716;
H. M. Fisher and R. C. Stoufer, Inorg. Chem., 1966, 5, 1172; M. A. Robinson and T. J.
Hurley, J . Inorg. Nuclear Chem., 1966, 28, 1747.
173 B. N. Figgis, J. Lewis, F. E. Mabbs and G. A. Webb, J. Chem. SOC.( A ) ,1966,422.
174 R. Dingle, J . Mol. Spectroscopy, 1965, 18, 276.
M. Gerloch, J. Lewis, F. E. Mabbs, and A. Richards, Nature, 1966, 212, 809.
1 7 6 B.F. Hoskins, R. L. Martin, and A. H. White, Nature, 1966, 211, 627.
1 7 7 E.Frank and C. R. Abeledo, Inorg. Chem., 1966, 5, 1453; R. M. Golding, W. C.
Tennant, C. R. Kanekar, R. L. Martin, and A. H. White, J . Chem. Phys., 1966, 45,
2688; R. M. Golding and H. J. Whitfield, Trans. Paraday SOC.,1966, 62, 1713.
178 R. W. Adam, C. G. Barraclough, R. L. Martin, and G. Winter, Inorg. Chem.,
1966, 5, 346.
179 I,. N. Mulay and N. L. Hofmann, Inorg. Nuclear Chem. Letters, 1966, 2, 189.
View Article Online
BTABBS A N D M A C H I N : T H E T R A N S I T I O N E L E M E N T S 199
pentaene} the iron is seven-co-ordinatewith the group Y unco-ordinated.ls*
From infrared and Raman spectral studies on [M(NH3)6]3+ and [M(ND3)6]3f,
the skeletal vibrational modes have been assigned.ls1 On the basis of their
Faraday rotations the 24,100 and 32,900 cm.-l charge-transfer bands of

K,Fe(CN), have been assigned to the 2T20 -+ 2Tlzcand 2Tzg-+ 2T2utransi-
tions, respectively.ls2
Magnetic susceptibility and infrared spectral measurements on the com-
plexes [Fe(diars),X,](BF,), (X = C1, Br) have been interpreted in terms of a
tetragonally distorted spin-paired iron(IV) complex with trans-halides. 83
The magnetic interactions in the complexes MRuO,, Sr,RuO,, and
(BaBi6Sr1/B)R~03 (M = Sr, Ca, Ba) have been discussed in relation to the
structures of these cornple~es.~~4 In the solid state,
(NH,),[oS,oCll,]H20 is diamagnetic, but in aqueous solution paramag-
netism corresponding to four unpaired electrons has been observed. This
behaviour in solution was interpreted on the basis of a dimer .c- monomer
equilibrium.185 The preparation and characterisation of OsF, has been
described.186 The gas-phase infrared spectrum of OsO, has been interpreted
on the basis of a normal co-ordinate analysis.ls7
Cobalt, Rhodium, and Iridium.-Refluxing [(Ph,P),RhCl] with carbon
disulphide has led to the isolation of trans-[(Ph,P),Rh(CS)Cl]which in turn
can be oxidised with chlorine to [(Ph3P),Rh(CS)Cl,].18s Rhodium-boron
bonds are reported to occur in compounds of the type [L,Rh(CO)X*BY,]
(X = Y = C1, Br; L = Ph3P or Ph,As).lsS The reaction between
[Co(CN)J3- and sulphur dioxide or stannous chloride has led to the isolation
of the complexes [(NC),Co-A-Co(CN),]6- (A = SO, or SnCl,), which contain
either Co-S-Co or Co-Sn-Co linkages.190 Sulphur dioxide has been shown
to addreversiblyto compounds of the type [MCl(CO)(Ph,P),] (M = Rh, Ir).lgl
A number of hydrido- and deuterio-iridium complexes, containing triphenyl-
phosphine and carbon monoxide as other ligands, have been prepared and
characterised using infrared and n.m.r. spectroscopy.lg2 Complexes of the
type [M(dp),]X [dp = C2H,(PPh,),; M = Co, X = ClO,; M = Ir, X = C1,
Br, I, ClO,, BPh,] have been shown to add hydrogen, hydrogen halides,
carbon monoxide, and sulphur dioxide. The iridium complexes add mole-
cular oxygen reversibly, whereas the cobalt complex was oxidised to
cobalt(II).l 9 3
S. M. Xelson, P. Bryan, and I). H. Busch, Chem. Comm., 1966, 641.
W. P. Griffith, J . Chem. SOC.( A ) ,1966, 899.
lS2 P. J. Stephens, Inorg. Cltem., 1965, 4, 1690.
lS3 G. S. F. Hazeldean, R. S. Nyholm, and R. V. Parish, J. Chem. SOC.
( A ) ,1966, 162.
la4 A. Callaghan, C. W. Moeller, and R. Ward, Inorg. Chem., 1966, 5, 1572.
lS6 B. Jesowska-Trezebiatowska, J. Hanuza, and W. Wojciechowski, J . Inorg.
Nmlear Chem., 1966, 28, 2701.
lS6 0. Glemser, H. W. Roesky, K.-H. Hellberg, and H.-U. Werther, C h e w Ber.,
1966, 99, 2652.
I. W. Levin and S. Abramowitz, Inorg. Chem., 1966, 5 , 2025.
M. C. Baird and G. Wilkinson, Chem. Comm., 1966, 267.
P. Powell and H. Noth, Chem. Comm., 1966, 637.
l S 0A. A. VEek and F. Basolo, Inorg. Clzem., 1966, 5, 156.
lgl L. Vaska and S. S. Bath, J . Amer. Chent. Soc., 1966, 88, 133.
lS2L. Vaska, Chem. Comm., 1966, 614; R. C. Taylor, J. F. Young, and G . Wilkinson,
Inorg. Chem., 1966, 5, 20.
l v 8A. Sacco, M. Rossi, and C. F. Nobile, Chem. Comm., 1966, 589.
View Article Online
The existence of an electron-transfer series of the type [MD,]* (D = di-

anion of o-phenylenediamine; M = Co, Ni, Pd, P t ; x = -2, - l , O , 3-1, +2)
has been demonstrated, and some of the members of the series is01ated.l~~
A series of complexes [(n-C,Hg)4N][M(S,C6X,Y2),] (M = Co, Ni, Cu;

X = Y = H, Me, Cl, or X = H, Y = Me) have been isolated, and their
spectral and magnetic properties shown to be consistent with a molecular
orbital energy scheme in which the highest filled orbitals are largely ligand
in cornpo~ition.~~5
The complex [Co(paphy)Cl,] [paphy = 1,3-bis-(2-pyridy1)-2,3-diazaprop-
l-ene] has been isolated as a- and /3-modifications. An X-ray structure
determination has shown the 8-form to be a five-co-ordinatemonomer with
essentially square-pyramidal geometry, whereas magnetic and spectral data
for the cc-form are consistent with an octahedral s t r ~ c t u r e . ~ ~
The
6 ligand
tris-(2-dimethylaminoethyl)amine(tren Me) forms high-spin five-co-ordinate
complexes of the type [M(tren Me)X]X [M = Co(n), Ni(n), Cu(rr); X = Cl,
Br, I, NO,, ClO,] which are thought to have trigonal-bipyramidal struc-
t u r e ~ .The
~ ~proton
~ nuclear magnetic resonance contact shifts for com-
plexes [CoL,X,] [L = py, (Me,N),PO; X = C1, Br, I, NCS] and [ML,]
M = Co, Ni; L = isoquinoline 2-oxide, quinoline l-oxide) have been inter-
preted in terms of unpaired electron spin delocalisation through cr- and/or
n-bonding mechanisms.lg8 Similar contact shift measurements for the
complexes [M(acac),]- and [M(acac),(pyNO),](M = Co, Ni) have been inter-
preted in terms of electron delocalisation. The results were also used to
estimate the magnetic anisotropy of
[Co(acac),]- (KII- K L = -4280 x c.g.s.u. mole-l) and the M-0-N
angle (114-125') in the pyN0 complexes.199
The structures of complexes of the types [Co L6]& ,O0 (L = hydrazine,
NN'-dimethylacetamide, di-2-pyridylamine,3-substituted urea ;X = halide,
C104, NO,) and [CoL,X,j ,01 ( L = NN-dimethylthioacetamide, 4,4'-diethoxy-
carbonyl-3,3',5,5'-t etrameth yldipyrromethane, E -thio caprolact am, substi-
tuted pyridines, a-benzylene-2,1-benzimidazole, substituted thiourea ; X =
halide, NCS, NO,) have been inferred from magnetic and spectral measure-
194 A. L. Balch and R. H. Holm, J. Arner. Chem. SOC.,1966, 88, 5201.
lS5 M. J. Baker-Hawkes, E. Billig, and H. B. Gray, J. Amer. Chem. SOC.,1966, 88,
4870.
1 9 6 I. G. Dance, M. Gerloch, J. Lewis, F. S. Stephens, and F. Lions, Nutzcre, 1966,
210, 295.
1 9 7 M. Ciampolini and N. Nardi, Inorg. Chern., 1966, 5, 41.
198R. W. Kluiber and W. Dew. Horrocks, jun., J. Amer. Chem. SOC.,1966, 88,
1399; B. €3. Wayland and R. S. Drago, ibid., p. 4597.
l S 9R. W. Kluiber and W. Dew. Horrocks, jun., J . Amer. Chern. SOC.,1965, 87,
5350; W. Dew. Horrocks, jun., R. H. Fischer, J. R. Hutchinson, and G. N. LaMar,
ibid., 1966, 88, 2436.
ZOOM. Goodgame, J. Chem. SOC.( A ) , 1966, 63; D. Nicholls, M. Rowley, and R.
Swindells, ibid., p. 950; P. S . Gentile and T. A. Shankoff, J . Inorg. Nuclear Chem.,
1966, 28, 1283; S. K. Madan and A. M. Donohue, ibid., p. 1617; J. A. Costamagna and
R. Levitus, ibid., p. 2685; B. B. Wayland, R. J. Fitzgerald, and R. S. Drago, J. Amer.
Chem. Xoc., 1966, 88, 4600.
201 J. deO. Cabral, H. C. A. King, S. M. Nelson, T. M. Shepherd, and E. Koros,
J, Chem. SOC.( A ) ,1966, 1348; J. Ferguson and B. 0. West, ibid., p. 1569; S . K. Madan
and D. Mueller, J. Inorg. Nuclear Chem., 1966, 28, 177; S. K. Madan and C. Goldstein,
ibid., p. 1251; G . Yagupsky, R. H. Negrotti, and R. Levitus, J. I n o r g . Nuclear Chaem.,
1965,27,2603; M. S. Elder, G. A. Melson, and D. H. Busch, Incwg. Chem., 1966,5,74.
View Article Online
M A B B S A N D M A C H I N : THE TRANSITION E L E M E N T S 201
ments. The formation of octahedral cobalt(=) and tetrahedral cobalt(n)
and copper(11) azido-complexes in methyl cyanide, dimethyl sulphoxide,
and trimethyl phosphate has been demonstrated.202 The infrared spectra of
(Et4N),[Co(N,),] and (Et,N),[Zn(N,),] in the solid state indicata a non-

linear M-N-N linkage.203 From similar studies on [M(~U)~X,] (M = Go, Zn,
Cd; X = C1, Br, I; t u = thiourea), ~ i ( t u ) , ] X , (X = Br-, NO,-), and
[Ni(tu),Cl,], metal-sulphur and metal-halogen stretching frequencies have
been identified.204 A study of the spectral and magnetic properties of
solutions of bis-(8-keto-amino)cobalt (n) complexes show that a planar
(S = 8) + tetrahedral (8 = 3/2) configurational equilibrium exists.205
The electronic spectra of the complexes [Co(amine),X,] (X = C1, Br, I,
NCS, NCSe) are virtually independent of the amine, except when they con-
tain a-substituted pyridines which decrease the supposed 4B2-+ 4A, transi-
tion by as much as 1000 cm.-1.206 Although the free ligand dithioacetyl-
acetone is not known, it has been stabilised in the complexes [M(SacSac),]
[M = CO(II), Ni(rr), Pd(n), Pt(n); SacSac = dithioacetyla~etonatoo].~~7 A
tetrameric complex, [co,o( OCOCMe,)6], for which the magnetic moment
indicates magnetic exchange interactions between the cobalt atoms, has
been isolated.208
The absolute configurations of the complexes a-(+)-tris-L-alaninato-
+
Co(m) ,09 and ( )-cis-dinitrobis-(-)-propylenediamine-Co(m) chloride
have been determined by single-crystal X-ray determinations and correlated
with their circular dichroism spectra. The circular dichroism, optical,
and optical rotatory dispersion spectra of a number of cobalt(111) ethylenedi-
amine, propylenediamine, cyclohexanediamine, and NNN'N'-tetrakis-(Z-
aminoethy1)-1,2-diaminoethane complexes 211 and of [CoX,I2- (X = C1,
Br, I) have been reported and discussed in terms of the ligand-field
symmetries and configurational effects. The isolation of geometrical isomers
of a number of tris-bidentate and hexa-co-ordinated mixed ligand cobalt(m)
complexes have been reported, and in some cases their electronic spectra are
discussed.21
203 V. Gutmann and 0. Leitmann, Monalsh., 1966, 9'9, 926.

203 D. Forster and W. Dew. Horrocks, jun., Inorg. Chem., 1966, 5, 1510.
204 C. D. Flint and M. Goodgame, J. Chem. SOC.( A ) ,1966, 744.
205 G. W. Everett, jun., and R. H. Holm, J . Amer. Chem. SOC.,1966, 88, 2442.
206 A. B. P. Lever and S. M. Nelson, J. Chem. SOC.( A ) ,1966, 859.
207 R. L. Martin and I. M. Stewart, Nature, 1966, 210, 522.
208 A. B. Blake, Chem. Comm., 1966, 569.
209 M. G. B. Drew, J. H. Dunlop, R. D. Gillard, and D. Rogers, Inorg. Chem., 1966,
5, 42.
210 G. A. Barclay, E. Goldschmied, N. C. Stephenson, and A. M. Sargeson, Chem.
Cornm., 1966, 540.
211 B. E. Douglas, Inorg. Chem., 1965, 4, 1813; H. L. Smith and B. E. Douglas,
Inorg. Chem., 1966, 5, 784; R . S. Treptow, ibid., p. 1593; A. J. McCaffery, S. F. Mason,
and B. J. Norman, Chem. Comm., 1966, 661; J. R. Gollogly and C. J. Hawkins, ibid.,
p. 873; S. F. Mason and B. J. Norman, J. Chem. Sbc. ( A ) ,1966, 307; C. J. Hawkins,
E. Larsen, and I. Olson, Acta Chem. Scund., 1965, 19, 1915.
212 R . G. Denning, J. Chem. Phys., 1966, 45, 1307.
213 E. Larsen and S. F. Mason, J. Chem. SOC. ( A ) ,1966, 313; K. Garbett and R. D.
Gillard, ibid., p. 802; J. H. Dunlop, R. D. Gillard, and R. Ugo, ibid., p. 1540; J. I. Legg
and D. TV. Cooke, Inorg. Chem., 1966, 5, 594; M. D. Alexander and D. H. Busch, ibid.,
p. 602; R. G. Denning and T. S. Piper, ibid.,p. 1056; B. E. Bryant, H. J. Hu, and W. H.
Glaze, ibid., p. 1373; N. Matsuoka, J. Hidaka, and Y. Shimura, Bull. Chem. SOC.Japan
View Article Online
The preparation, and assignment of structures from spectroscopic

measurements, of complexes of the types [Co(tetram)XY]+ (tetram is a
cyclic quadridentate-amine ; X and Y can be halide or pseudo-halidegroups),
[Co en2&YIn+(X = a primary aliphatic amine; Y = C1, Br or X = glycin-

ato, Y = Cl), [Co(dmg),XL] (dmg = dimethylglyoximato; X = thiourea;
L = mono-deprotonated thiourea), and trans-[Rh en,X2]N03 (X = C1, Br)
have been rep0rted.2~~The peroxy-bridged complexes trans-[X(cyc1am)Co-
O,Co(cyclam) XI2+ (cyclam = 1,4,8,11-tetra-azacyclotetradecane; X = C1,
N3,NCS, NO,) have been isolated and converted into trans-[Co(cyclam)XY]+
by reaction with acids HY.216 An X-ray structural study of the complex
[(NH3),Co02Co(NH,)],(S0,)HS0,), has been interpreted in terms of a
bridging superoxide (02-)rather than a peroxide group.216
The preparations of some hydrido-complexes, [RhH(NH,),]SO,,
[RhH(H20)(NH,)4]S0,,217K2[RhH(CN)4H20],21g [IrHxY3-,L,] (x = 1,2, or
3; Y = halogen; L = R3P, R,As), [IrH,(PR,),],219 and [IrH,(PMe,Ph),]
(Y = C1, Br, I, H, CN, SCN),220have been given, and infrared and n.m.r.
spectra used to determine stereochemistries. The infrared spectra of some
bis-ethylenediamine-cobalt (III), halogeno-iridium(m) arsine or phosphine
complexes, [RhCl,,SRCN], [RhCl,(TPP)], and [MX,(TPP),] (M = Pd, Pt,
Hg; X, C1, Br; TPP = 1,2,54riphenylphosphole)have also been discussed
in relation to the possible structures of the complexes.22l
Nickel, Palladium, and Plathum.-The compounds of stoicheiometry
Pt(PPh,) and Pt(PPh,), have been prepared, and the mono-derivative is
shown to be tetrameric in benzene solution.222 A new and convenient
preparation of Ni(PF3)4from nickelocene and PF, has been reported.223
The reaction of Pt(PPh,), with hydrochloric acid has been shown to give a
series of hydride complexes, whereas the corresponding palladium and nickel
complexes, and [M(Ph,P(CH2)2PPh2),](M = Ni, Pd, Pt), gave only hydro-
gen.224 The reaction between Pt(PPh,), and CS, or COS resulted in the
isolation of monomeric compounds, [(Ph,P),Pt L] (L = CS,, COS).225
1966, 39, 1257; K. Ohkawa, J. Hidaka, and Y. Shimura, ibid., p. 1715; M. Shibatu,
H. Nishikawa, and Y. Nishida, ibid., p. 2310; T. P. Emmenegger and G. Schwarzenbach,
Helv. Chim. Acta, 1966, 49, 625; F. P. Dwyer, I. K. Reid, and A. M. Sargeson, Austral.
J . Chem., 1965, 18, 1919; J. A. Broomhead, Nature, 1966, 211, 741.
214 S. C. Chan and F. Leh, J. Chern. SOC.( A ) , 1966, 760; P. 0. Whimp and N. F.
Curtis, ibid., p. 867; J. P. Collman and P. W. Schneider, Inorg. Chem., 1966, 5, 1380;
M. D. Alexander and D. H. Busch, ibid., p. 1590; A. V. Ablov, B. A. Bovykin, and
N. M. Samus, Russ. J. Inorg. Chem., 1966, 11, 31; R. D. Gillard, E. D McKenzie, and
M. D. Ross, J . Inorg. Nuclear Chern., 1966, 28, 1429.
215 B. Bosnich, C. K. Poon, and M. L. Tobe, Inorg. Chem., 1966, 5, 1514.
216 W. P. Schafer and R. E. Marsh, J. Arner. Chem. SOC., 1966, 88, 178.
217 J. A. Osborn, A. R. Powell, and G. Wilkinson, Chem. Comm., 1966, 461.
218 D. N. Lawson, M. J. Mays, and C . Wilkinson, J. Chem. SOC.( A ) ,1966, 52.
21g J. Chatt, R. S. Coffey, and B. L. Shaw, J. Chem. Soc., 1965, 7391.
2 2 0 J. M. Jenkins and B. L. Shaw, J. C h m . SOC.( A ) ,1966, 1407.
821 R. A. Walton, J. Chem. SOC.( A ) , 1966, 365; J. M. Jenkins and B. L. Shaw,
J . Client.SOC.,1965,6789; M. N. Hughes and W. R. McWhinnie, J. Inorg. Nuclear Chem.,
1966, 28, 1659; B. F. G. Johnson and R.A. Walton, ibid., p. 1901,
Z z 2 R. Ugo, F. Cariati, and G. LaMonica, Chem. Comm., 1966, 868; R. D. Gillard,
R. Ugo, F. Cariati, S. Genini, and F. Bonati, ibid., p. 869.
223 J. F. Nixon, Chem. Comrn., 1966, 34.
2 2 4 F. Cariati, R . Ugo, and F. Bonati, Inorg. Chem., 1966, 5 , 1128.
2 2 6 M. C. Baird and G. Wilkinson, Chem. Comm., 1960, 614.
View Article Online
MABBS AND MACHIN: THE T R A N S I T I O N E L E M E N T S 203
Diamagnetic, square-planar dithiolate complexes [M(dt)2]2- [M = Ni,
Pd, Pt, Cu; dt = S2CS2-, S2CNCN2-, S2CC(CN)22-]have been isolated.Z26
It bas been proposed that the occurrence of isotropic g-values close to the
free-electron value, in complexes of the type [Ni(mnt),]-, is diagnostic

evidence for the presence of cation-stabilisedfree radicals.227 The existence
of an electrontransfer series of general formula [MLJ (M = Ni, Co, Cu,
Zn, Cd; L = catechol, tetrachlorocatechol) has been demonstrated using
electrochemical oxidation, e.s.r., and chemical methods.22* The complexes
C]SI(S,C,Ph,),] (M = Ni, Pd) react with Ph,P(CH,),PPh,(diphos) to give
compounds [M(S2C,Ph2)(diphos)], whereas the corresponding platinum com-
pound only gives an adduct, [Pt(S,C,Ph,),(diphos)]. 229
The low-temperature single-crystal polarised spectrum of K2PtC14230 and
the circular dichroism of the [PtC1,I2- ion 231 have been discussed in relation
t o their structures. A discussion of the effect of a distant asymmetric centre
on the circular dichroism of the complexes truns-[PdCl,(-)amz] and trans-
[PdCl,( -)amz] (am = l-phenylethylamine) has also been given.232
The effect of spin-orbit coupling, an axial ligand-field component, and
an orbital reduction factor, k, on the magnetic properties of the 3T1term
has been calculated, and the results are used to interpret the observed
magnetic behaviour of a series of tetrahedral Ni(n) cornple~es.23~The
diamagnetism of [Ni(diarsine),](ClO,), has been interpreted on the basis of
an octahedral arrangement of ligands, which has electrical symmetry of D,,
arising from 0- and n - b ~ n d i n g .The
~ ~ ~crystal-field terms which arise for
nickel(@ in trigonal-bipyramidal and square-pyramidal stereochemistries
have been calculated, and the predicted spectral transitions found to be in
satisfactory agreement with those 0bserved.~~5The effects of clustering,
and of exchange interactions between nickel@) ions in some Perovskite
fluoride complexes, on the electronic absorption spectra are reported.236
The proton magnetic resonance contact shifts in a number of nickel@)
Schiff base, nitrogen and oxygen donor, and diphosphine complexes have
been used to suggest possible modes of electron-spin delocalisation and the
existence equilibria between complexes with different stereochemistries.237
2z6 J. P. Fackler, jun., and D. Coucouvanis, J . Amer. Chem. SOC.,1966, 88, 3913;
R. G. Werden, E. Billig, and H. B. Gray, Inorg. Chem., 1966, 5, 7 8 .
2 2 7 A. H. Maki, T. E. Berry, A. Davidson, R. H. Holm, and A. L. Balch, J . Amer.
Chem. SOC.,1966, 88, 1080.
2 2 8 F. Rohrscheid, A. L. Balch, and R. H. Holm, Inorg. Chem., 1966, 5, 1542.
2 2 g V. P. Mayweg and G. N. Schrawzer, Chem. Comm., 1966, 640.
2 3 0 D. S. Martin, jun., M. A. Tucker, and A. J. Kassman, Inorg. Chem., 1965, 4,
1682; 1966, 5, 1298.
231 B. Bosnich, J . Amer. Chem. SOC., 1966, 88, 2606; D. S. Martin, J. G. FOSS, M. E.
McCarville, M. A. Tucker, and A. J. Kassman, Inorg. Chem., 1966, 5 , 491.
232 B. Bosnich, J . Chem. Xoc. ( A ) , 1966, 1394.
233 B. N. Figgis, J. Lewis, F. E. Mabbs, and G. A. Webb, J . Chem. SOC. ( A ) ,1966,
1411.
a 3 4 B. Bosnich, R. Bramley, R. S. Nyholm, and M. L. Tobe, J . Amer. Chem. SOC.,
1966, 88, 3926.
2 3 5 M. Ciampolini, Inorg. Chem., 1966, 5, 35.
236 W. W. Holloway, jun., and M. Kestigian, J . Chem. Phys., 1966, 45, 639; J.
Ferguson and H. J. Guggenheim, ibid., p. 1095.
2 3 7 R. W. Kluiber and W. Dew. H O I T O C ~ , I w g . Chem., 1966, 5, 152; J. D.
jun.,
Thwaites and L. Sacconi, ibid., p. 1029; J. D. Thwaites, J. Bertini, and L. Sacconi,
ibid., p. 1036; G. R. van Hecke and W. Dew. Horroclm, jun., ibid., p. 1968; R. Holm
View Article Online
As with cobalt(@, infrared, electronic spectra, magnetic susceptibility,

molecular weight, and conductivity data have been used to suggest structures
for the following types of complexes: [ML,X,] (M = Ni, Pd, P t ; L can be
monothio-p-diketone, quinoline, isoquinoline, dimethylpyridines, 2-methyl-

benzimidazole, 3-methylis0quinoline, 2- methylbenzothiazole, 2-, 3- or
4-cyanopyridine; X can be C1, Br, I, NCS, dicyanamide, tricyanmethanide,
substituted pyridines, bipyridyl, substituted 1,lo-phenanthrolines) ;23*
[NiL,] (L = 1,5-diazacyclo-octane,Schiff bases derived from diketones and
aromatic amines or from salicylaldehydes and substituted trimethylene-
diamines);239 [INiLYX],nH,O {L = 2,12-dimethyl-3,7,11,17-tetra-azabicyclo-
[11,3,1]heptadeca-1(17),2,11,13,15-pentaene; Y = X = ClO,, n = 0 ;
Y = X = C1,n = 0 ; Y = X = NCS,n = 0 ; Y = X = Br,n = l ; Y = Br,
X = BF,, n = 1);24* [M,X,L] [M = Pd(rr), Pt(rr); X = Cl, Br, I, SCN;
L = 1,4-di-(o-aminothiophenoxy)but-trans-2-ene]. The occurrence of
diketones bonded through a carbon atom rather than the oxygena has been
reported in complexes of the type [Pt(diketone),X]- (X = C1, Br). These
complexes can then co-ordinate, through the diketone oxygen atoms, to
other transition metals to give compounds of the type M[Pt(acac),X],
(M = Mn, Fe, Co, Ni, Cu, Zn, Cd, Pd).,,, The isolation of compounds
K3Ni(CN),,2H,0 and Mvi(CN),],2H20 {M = [Cr(NH,),I3+, [Cr en3I3+},
which contain the [Ni(CN),]3- ion, and the stability of this ion towards
decomposition to [Ni(CN),]2- has been reported. 243
A number of palladium(n), platinum(II), cadmium(n), and mercury(n)
halide and silver(1) perchlorate complexes with the ligands Ph3PSe and
Ph,AsS have been prepared and their infrared spectra discussed with respect
t o P-Se and As-S stretching vibrations. Platinum-silicon and platinum-
germanium bonds have been reported to occur in the complexes
[Me3M-Pt(C1)(PEf3),](M = Si, Ge),245 whilst the Pr,Sn, cluster is thought
to be present in the ion [Pt3Sn,C1,,]4-.246 A cyclic structure, in which
approximately square-planar NiS, units form the faces of it hexagonal prism,
has been proposed for [Ni(SR),], comp0unds.~4~Infrared absorption bands
G. W. Everett, jun., and W. Dew. Horrocks, jun., J. Anzer. Chem,.SOC.,1966, 88, 1071;
B. B. Wayland, R. S. Drago, and H. F. Henneike, ibid., p. 2455; L.Morpurgo and
R. J. P. Williams, J. Chem. SOC.( A ) , 1966, 73.
238M. Goodgame and M. J. Weeks, J . Chem. Soc. ( A ) , 1966, 1156; P. L. Goggin
and R. J. Goodfellow, ibid., p. 1462; R. A. Walton, J . Inorg. Nuclear Chem., 1966, 28,
2229; L. Sacconi and I. Bertini, Inorg. Nuclear Chem. Letters, 1966, 2, 29; S. H. H.
Chaston, S. E. Livingstone, and T. N. Lockyer, Austral. J. Chem., 1966, 19, 1401;
H. Kohler, H. Hartung, and B. Seifert, 2. Anorg. Chem., 1966, 34'7, 30.
239 W. K. Musker and M. S. Hussain, Inorg. Chem., 1966, 5, 1416; L. Sacconi,
N. Nardi, and F. Zanobini, ibid., p . 1872; S . Yamada, H. Xshikawa, and E. Yoshida,
Bull. Chern. SOC. Japan, 1966, 39, 994.
2 4 0 J. L. Karn and D. H. Busch, Nature, 1966, 211, 160.
z41D. C. Goodall, J. Chem. Soc. ( A ) ,1966, 1562.
2 4 2 J. Lewis, R. F. Long, and C. Oldham, J. Chem. SOC.( A ) ,1965, 6740; D. Gibson,
J. Lewis, and C. Oldham, J. Chem. SOC.( A ) ,1966, 1453.
2 4 3 W. C. Andersen and R. H. Harris, Inorg. Nuclear Chem. Letters, 1966, 2, 315;
K. N. Raymond and F. Basolo, Inorg. Chem., 1966, 5, 949.
2 4 4 P. Nicpon and D. W. Meek, Chem. Comm., 1966, 398.
2 4 5 F. Glockling and K. A. Hooton, Chem. Comm., 1966, 218.
R. V. Lindsey, jun., G. W. Parshall, and V. G. Stolberg, Inorg. Chern., 1966,5, 109.
E. W. Abel and B. C. Crosse, J. Chem. Soc. ( A ) ,1966, 1377.
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MABBS A N D M A C H I N : THE T R A N S I T I O N E L E M E N T S 205
have been assigned to the various vibrational modes in nickel@), palla-
dium(=), and copper(n) bis-(oxamido)-complexes,24~t o metal-nitrogen
stretching vibrations in palladium(11), platinum(=) and rhodium(m) halide
MeCN, PhCN, and bipyridyl cornple~es,~4~ and t o stretching vibrations of

the azide group in the compounds [Ph4As]2[Pt(N3)4]H20, [Ph,As],[Pt(N,),],
and [Ph,As][Au(N,),]. The magnetic data, electronic and infrared spectra
of Rb,~i(NO,),] were reported t o be consistent with a distorted octahedral
structure involving nitrogen co-ordinated and either chelating or symmetri-
cally bridging nitrite groups. 251 Similar spectra measurements indicate the
presence of nitro groups in the complexes [NiL,(NO,),] (L = a substituted
ethylenediamine), although in chloroform solution some of the complexes
showed a n equilibrium between nitro and nitrito groups.252
The complex (NO,+)[Ni(NO,),], which has peE= 4-54 B.M. a t 21"c,
was reported to be the first known example of a high-spin Ni(m) c0mplex.~5~
The reaction between palladium and nitric acid has been shown to give
[Pd(NO,),(OH),], which can then react with N204t o give [Pd(N03),2N204],
or with N,O, to give the simple nitrate, Pd(N0,),.254 The reaction between
bromine trifluoride and the compounds M,[PtCl,] (M = K,Rb,Cs,NO+)
gave M',[PtC13F3], except in the case of M = NO+, when (NO),[PtF,] was
formed.255 The infrared and Raman spectra of K,[Pt(CN),Cl,] were re-
ported, and the force constants for bond stretching c a l c ~ l a t e d . ~ 5The
~
preparations and magnetic properties of the compounds M[PtF,] (M = XeF,,
NO, NO,) have been described.257 The reaction between PtF, and ClF,
gave a compound which infrared data suggest should be formulated as
[ClF,] +[PtF,]-. With PtF, and tetrafluorohydrazine, PtF, and PtF4 were
produced succe~sively.25~
Copper, Silver, and Gold.-The infrared and Raman spectra of compounds
containing the ions [Cu(CN),]-, [CU(CN),]~-, and [Cu(CN)JS- have been
discussed in terms of possible stereochemistries and modes of bonding in
these ions.259 Infrared spectral studies on pressed discs of KBr and
KAu(CN), showed that solid solutions were not formed, but that [Au(CN),]-
groups remained in clusters.260 The preparations of complexes of the type
[ML,]X (L = 8-methylthioquinoline, 8-benzylthioquinoline ; M = Cu, Ag ;
248 P. X. Armendarez and K. Nakamoto, Inorg. Chem., 1966,5, 796.

249 R. A. Walton, Canad. J . Chem., 1966, 44, 1480.
250 W. Beck, E. Schuierer, and K. Feldl, Angew. Chem., Internat. Edn., 1966, 5,
249.
251 B. J. Hathaway and R. C. Slade, J . Chem. SOC.( A ) ,1966, 1485.
252 D. M. L. Goodgame and M. A. Hitchman, Inorg. Chem., 1966, 5, 1303.
253 C. C. Addison and B. G. Ward, Cl2em. Cornrn., 1966, 819.
2 5 4 C. C. addison and B. G. Ward, Chem. Cmm., 1966, 155.
2 5 5 D. H. Brown, K. R. Dixon, and D. W. A. Sharp, J . Chem. SOC.( A ) , 1966,
1844.
256L. H. Jones and J. M. Smith, Inorg. Chem., 1965, 4, 1677.
257T. I?. Gortsema and R . H. Toeniskoetter, Inorg. Chern., 1966,5, 1217; N. Bartlett
and S. P. Beaton, Chem. Cotnm., 1966, 167; N. Bartlett, F. Einstein, D. F. Stewart,
and J. Trotter, ibid., p. 550.
258 F. P. Gortsema and R. H. Toeniskoetter, Inorg. Chem., 1966, 5, 1925.
2 5 9 D. Cooper and R. A. Plane, Inorg. Chem., 1966, 5, 16; J. D. Graybeal and G . L.
McKown, ibid., p. 1909; M. J. Reisfeld, and L. H. Jones, J. ~ W o lSpectroscopy,
. 1965,
18,222.
2 6 0 L. H. Jones and I K. Kressin, J . Chem. Phys., 1965, 43, 3956.
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206 I N O R G A N I C CHERTISTRY
X = ClO,) have been described.261 The characterisation and suggestions

for the structure of the ion [Au,(DPE),cl]+ (DPE = 1,2-bisdiphenylphos-
phinoethane) have been reported. 262 The reaction between [(Ph,P),CuBH,]
and perchloric or tetrafluoroboric acids resulted in compounds containing the

[(Ph3P)2Cu(BH,)Cu(PPh3)2]+ ion, for which it structure with four bridging
hydrogens between the copper and boron atoms was pr0posed.~6~The
presence of carbon bonded acetylacetone has been demonstrated in the
compounds [( R , P ) A ~ ( a c a c ) ] .The
~ ~ ~rapid evolution of carbon dioxide from
solutions of CuCl and CCl, in Me2S0 has been interpreted in terms of the
following reactions :265
8CuCl + CCI, + Me,SO = [4cu(I) + ~ C U ( I I )+ 12C1-] + CO + Me,S
CO + Me,SO = CO, + Me,S
The preparations of [(Et,P)Au Y] [Y = alkyl or aryl mercaptides, SCN,
SC(S)NEt,, SC(S)OEt, SC(NH,)&E€, +Br-1, [(PhO),PAuCl], [(R3P),Au] +
(R = Et or Ph), and [R,Au XI (R = Bu, Ph; X = C1, Br, SCN) have been
described.266
The magnetic susceptibilitiesof the following compounds have been inter-
preted in terms of their probable structures and the occurrence of magnetic
exchange interactions (in some cases estimates of the magnitudes of these
interactionsihavebeen made) :{Cu(02C[CH,],C02)};267[(R,N)CU(CH,CO,)~X]
(X = NCS, NO,, Br);268[Cu(RR’CHCO,),] (R = R’ = Et; R = H and
R’ = CN, MeO, EtO, PhO, CT-ClC6H40, p-NO,C,H,O) ;269 [CU(X-CGH,CO2)2-
(butanol)] (X = H, p-Me, p-MeO, p-Br, p-N02);270[CuL2X2]and [CuLX,]
(L = substituted pyridine N-oxide; X = halide),271 [Cu(AO)X] A 0 =
amino-alcoholates; X = halide) ;2’2 bis-(imidazolato)Cu(~~),~~~and X-sal-c-
aminophenol)Cu(11).274 I n the copper acetate dimer support for the &bond-
ing model for the metal-metal interaction has been obtained from 63Cu
nuclear magnetic resonance.275
Molecular orbital calculations on some bis-(p-diketone)Cu(n)complexes
have been reported, and the results compared with e.s.r. and electronic
spectral measurements.276 Similarly, molecular orbital calculations have
261 F. Hein and K.-H. Vogt, Annalen, 1965, 689, 202; F. Hein and K.-H. Vogt,
2.anorg. Chem., 1965, 340, 46.
262 L. Naldini, F. Cariati, G. Simonetta, and L. Malatesta, Chem. Comm., 1966, 647.
263 F. Cariati and L. Naldini, J . Inorg. Nuclear Chem., 1966, 28, 2243.
2 6 4 D. Gibson, B. F. G. Johnson, J. Lewis, and C. Oldham, Chem. and Ind., 1966,342.
2 6 5 R. R. Lavine, R. T. Iwamoto, and J. Kleinberg, J . Amer. Chem. SOC., 1966, 88,
4304.
366 (x. E. Coates, C. Kowala, and J. M. Swan, AustmE. J . Chem., 1966, 19, 539.
267 L. Dubricki, C. M. Harris, E. Kokot, and R. L. Martin, Inorg. Chem., 1966, 5,
93; B. N. Figgis and D. J. Martin, ibid., p. 100.
2 6 8 D. M. L. Goodgame and D. F. Marsham, J . Chem. SOC.( A ) , 1966, 1167.
26D W. E. Hatfield, H. M. McGuire, J. S. Paschal, and R. Whyman, J . Chcm. SOC. (A),
1966, 1194.
2 7 0 W. E. Hatfield, C. S. Fountain, and R. Whyman, Inorg. Chem., 1966, 5, 1855.
2 7 1 W. E. Hatfield and J. C. Morrison, Inorg. Chem., 1966, 5, 1390; Y. Muto and
H. B. Jonassen, Bull. Chem. SOC.Japan, 1966, 39, 58.
2 7 3 E. Uhlig and K. Staiger, 2. anorg. Chem., 1966, 346, 21.
273 M. Inoue, M. Kiahita, and M. Kubo, Bull. Chem. SOC. Japan, 1066, 39, 1352.
2 7 4 W. E. Hatfield and F. L. Bunger, Inorg. Chem., 1966, 5, 1161.
D. J. Rogers, Inorg. Chem., 1965, 4, 1830.
2 7 6 H. C. Allen, jun., J. Chem. Phys., 1966, 45, 553; F. A. Cotton and J. J. Wise,
J . Amer. Chem. SOC.,1966,88, 3451; G. N. LaMar, Acta Chem. S c a d . , 1966,20, 1359.
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M A B B S A N D M A C H I N : THE T R A N S I T I O N E L E M E N T S 207
also been made for [cu(m3)6]2+9[c~(H,o),]~+, and copper(II)in tetrahedral,
square-planar, and octahedral chloride environments.277 The interpretation
of the optical and e.s.r. spectra of [CuC1,I2-, dissolved in Cs,ZnCl, and
(Me4N),ZnC1, host lattices, has led to the proposal that the low symmetry
of the ion is an intrinsic property, for which the dominant mechanism is the
Jahn-Teller effect.278
Quinqueco-ordinated copper(n) was reported to occur in the complexes
[X-salen-N(R)R’],Cu (R = H orMe and R’ = Me), [Cu(mepic),X](ClO,)
(mepic = 6-methyl-2-picolylamine; X = halide), [(A)Cu-(CN)-Cu(A)](C1O4),
(A = hexamethyltetra-azacyclotetradecadiene),27sand [Cu(bipy),X] (X =
halide). This last compound is thought to have a compressed trigonal-
bipyramidal structure. Based on spectral and magnetic evidence, tetra-
gonally distorted octahedral structures have been assigned to the complexes
[Cu(NH,),]X, (X = C1-, Br-, I-, BF4-, ClO,-) and [Cu(ben~imidazole)~X,]
(X = C1, Br, NO,, ClO,, NCS, +SO,).2s1
The Raman spectra of powdered samples and solutions of compounds
containing the ions [MX,]”- (M = Au; X = C1, Br, I; n = 1 : M = Pt:
X = C1, Br, I; n = 2: M = Pd; X = C1, Br; n = 2) have been examined
and M-X stretching force constants estimated. 282 The compound
Cs,K[AgF,] has been prepared and its magnetic moment reported t o be
2.6 BM.,83
Zinc, Cadmium, and Mercury.-The bond stretching force constants
El(Hg-Hg), E,(Hg-X) and the interaction constant, El,, between adjacent
bonds in the compounds Hg,X, (where X = C1, Br H,O) have been estimated
from their Raman spectra. 284 The isolation of compounds Hg2L4(C10,),
[L = Ph,PO, pyN0, (CH,CH,CH,),SOJ, Hg,L,SiF, (L = Ph,PO,pyNO),
Hg,(Me,SO)SiE”,,xH,O, Hg2(Me,SO),.,(C10,), and HgNO, has been re-
ported.2s5 Metal-phosphorus vibrations in the complexes [(Ph,P),MX,]
(M = Zn, Cd, Hg; X = C1, Br, I) have been assigned to bands in the
98-166 cm.-l region.286 Frequency assignments have also been made from
the Raman spectra of [M en,]X, (M = Zn, Cd, Hg; X = and
of aqueous solutions of Hg(CN), and halide ions.,g8
The preparations of 1 : 1 addition compounds between 1,3,5-trithian9
HgX, (X = C1, Br, I), and AgX (X = NO,, C1, Br, I)2s9and of the com-
plexes [ZnB,X,], [ZnB,X,], [ZnB,X,] (B = py, 4-Me py, %Me py; X = C1,
2 7 7 P. Ros and G. C. A. Schuit, Theor. Chim. Acta, 1966, 4, 1; B. ROOS, A d a Chem.
Scand., 1966, 20, 1673.
2 7 8 M.Sharnoff and C. W. Reimann, J. Chem. Phys., 1965, 43, 2993.
2 7 9 Y. M. Curtis and N. T. Curtis, Awtral. J. Chem., 1966, 19, 609; L. Sacconi and
I. Bertini, Inorg. Chem., 1966, 5,1520; S . Utsuno and K. Sone, J . Imrg. Nuclear Chem.,
1966, 28, 2647.
2 s o H.Elliott, B. J. Rathamay, and R. C. Slade, J . Chem. SOC.( A ) ,1966, 1443.
2 8 1 M. Goodgame and L. J. B. Haines, J . Chem. SOC. ( A ) ,1966, 174; H. Elliott and
B. J. Hathaway, Inorg. Chem., 1966, 5, 885.
2 8 2 P. J. Hendra, Nutwe, 1966, 212, 179.
283 R.Hoppe and R. Homann, Naturwiss., 1966, 53, 501.
H. M. Gager, J. Lewis, and M. J. Ware, Chem. Comm., 1966, 616.
2 8 6 R.A. Potts and A. L. Allred, Inorg. Chem., 1966, 5, 1066.
286 G. B. Deacon and J. H. S. Green, Chem. Comm., 1966, 629.
2 8 7 K. Krishnan and R. A. Pla.ne,Inorg. Chem., 1966, 5, 852.
2 8 * R. P. J. Cooney and J. R. Hall, J. Inorg. Nuclear Chem., 1966, 28, 1679.
J. A. W. Dalziel and T. G. Hewitt, J . Chem. SOC.( A ) ,1666, 233.
View Article Online
208 INORGAN%C CHENISTRY
Br, I, NCS)290have been described. From infrared spectra and the iso-
morphous inclusion of cobalt(I1) ions, it was concluded that [ZnB,X2],
[ZnB,X,], and [ZnB,X,] have tetrahedral, five-co-ordinate, and octahedral
structures, respectively. Mercury-silicon and zinc-germanium bonding is

reported in [(Ph,Si),Hg] 291 and [Zn(GePh,),],292 respectively.
290 . Chem., 1966, 19,
D. P. Graddon, K. B. Henig, and E. C. Watton, A u s t ~ a l J.
1801.
2Q1 R. A. Jackson, Chena. C m m . , 1966, 827.
2n2 E. Amberger, W. Stoeger,and R. Honigschmid-Grossich, Angew. Chem., Internat.
Edn., 1966, 5, 522.
View Article Online
5. TRANSITION-METAL CARBONYLS AND

RELATED COMPOUNDS
By F. J. Kohl and J. Lewis
(Department of Chemistry, University of Manchester)
THEtechniques for the preparation of metal carbonyls and olefin derivatives

have been summarised,l the reactions of ligands co-ordinated with transition
metals have been reviewed,2 the application of n.m.r. in organometallic
chemistry has been summarised,x and the chemistry of the Group VIB
carbonyls 4 and the nqture of sulphur- and phosphorus-bridged complexes
of the transition metals have been ~urveyed.~Reviews have appeared on
the cyclopentadiene and arene metal carbonyls,6 hydride complexes,‘
~ electronic structures of
nitrosyl-metal complexes,g metal c l ~ s t e r s ,the
organometallic molecules,1* and acylation reactions,l1 as well as fluorine
organometallic complexes,l2, 13 metal-ally1 complexes,l* and cyclic-organic
metal derivatives.l5 A n extensive survey of the chemistry of nickel-cyclo-
octadiene systems has been given.16
An English edition of “ Metal n-Complexes ” by Fischer and Werner has
been published;l7 books on metal hydrides l8 and benzoid-metal complexes
have also appeared. Seyferth and King have produced an annual survey of
organometallic chemistry, and this must be considered as one of the more
outstanding texts of the year;20 it provides a valuable service to the field.
Structure.-A theoretical assessment of the bonding in metal car-
bonyls 21 and unsaturated hydrocarbon derivatives of iron and chromium 22
H. F. Holtzclaw, jm., Inorg. Synth., 1966, 7, 178.
J. P. Collman, Transition Metal Chem., 1966, 2, 2.
S. L. Stafford and H. D. Kaesz, Adv. Organometallic Chem., 1965, 3, 1.
G. R. Dobson, I. W. Stole, and R. K. Sheline, Adv. Inorganic Chemzstry Radio-
chem., 1966, 8, 1.
ti R. G. Hayter, Preparative Inorg. Reactions, 1965, 2, 211.
* R. L. Pruett, Preparative Inorg. Reactions, 1965, 2, 187.
A. P. Ginsberg, Transition Metal Chem., 1965, 1, 112.
* B. F. G. Johnson and J. A. McCleverty, Progr. Inorg. Chem., 1966, 7, 277.
O F. A. Cotton, Quart. Rev., 1966, 20, 389.
l o D.A. Brown, Transition Metal Chem., 1966, 2, 2.
l 1 F. Calderazzo and K. Noack, Coordination Chem. Rev., 1966, 118; R. F. Heck,
Adv. Organometallic Chem., 1966, 4, 243.
l2 R. D. Chambers and T. Chivers, Organometallic Chem. Rev., 1966, 1, 279.
l 3 F. G.A. Stone, Endeavour, 1966, 25, 33.
l4 G. Wilke, B. Bogdanovid, P. Hardt, P. Heimbach, W. Keim, M. Kroner, W.
Oberkirch, K. Tanaka, E. Steinbriicke, D. Walter, and H. Zimmermann, Angew. Chem.,
1966, 78, 157.
l 5 P. M. Maitlis, Adv. Organometallic Chem., 1966,4,95; M. A. Bennett, ibid., p. 353;
H. Cais, Organometallic Chem. Rev., 1966, 1, 433.
l 6 B. Bogdanovic, M.Kroner, and G. Wilke, Annalen, 1966, 699, 1.
l 7 E.0. Fischer and H. Werner, “ Metal .rr-Complexes,”Elsevier, Amsterdam, 1966.
l 8 K. M. Mackay, “ Hydrogen Compounds of the Metallic Elements,” Spon, London,
1966.
l o H. Zeiss, P. J. Wheatley, and H. J. S. Winkler, “ Benzoid-Metal Complexes,”
Ronald Press, New York.
2 o D. Seyferth and R. B. King, Ann. Survey Organometallic Chem., 1965, 1.
21 S. F. A. Kettle, J. Chem. SOC. ( A ) ,1966, 1013, 420.
2 2 B. J. Nicholson, J. Amer. Chem. Soc., 1966, 88, 5156.
View Article Online
tri-carbonyl has been discussed. The carbonyl stretching frequencies in the

infrared spectra of complexes have been considered theoretically, and changes
in bonding forces shown to be associated with n-electron effects.23 The
intensity of both carbonyl and nitrosyl vibrations has been correlated to

the bond angle between the groups and the theory applied to an extensive
series of comp0unds.~4 The relative intensities of the two % vibrations of
compounds of the form XMh(CO), have been considered in terms of coupling
and distortionof bond anglesat themetal away from The low-frequency
spectra (700-200 cm.-l) of a series of manganese carbonyl derivatives
Mn(CO),L (L = halogen or alkyl) have been measured and discussed with
relation to the carbonyl stretching modes.26 Mass spectroscopic measure-
ments are now being extensively applied to organometallic and carbonyl
systems. The negative-ion mass spectra of nickel, iron, chromium, molyb-
denum, and tungsten carbonyl have been determined.2' The utilisation of
mass spectra in the determination of the number of hydrogen atoms in the
carbonyl hydrides of manganese, rhenium, and ruthenium has been empha-
sised,28 whilst the spectra of some polynuclear carbonyls and related com-
pounds of manganese, molybdenum, rhenium, iron, ruthenium, osmium, and
cobalt have been reported, and the fragmentation pattern associated with
the structure of these polynuclear cornpound~.2~-~~
The study of the kinetics of substitution reactions of the Group VI
carbonyls with a variety of phosphines, amines, and oligo-olefinshave shown
that the reactions proceed by an SNldissociative mechanism a t low ligand
concentrations ( <0.025~),53whereas at higher concentrations ( > 0 . 0 5 ~ )
phosphine exchange occurs by a dual path involving an additional SN2
mechanism.34 The kinetics of mono- and di-substitution of mcyclopenta-
dienylrhodium dicarbonyl by phosphines, phosphites, and isonitriles show
that the reaction is first-order in substrate and a reagent.35 The data on
the exchange of carbon monoxide and triphenylphosphine with nickel
carbonyl have been reassessed and indicate that the reaction proceeds by a
non-dissociative first-order process.36
The structure of iron dodecacarbonyl has finally been resolved in the
solid state by X-ray diffraction, and is, as suggested in the previous Annual
Reports, a triangular metal cluster in which one bridging group of the
2s S. F. A. Kettle, Spectrochim. Acta, 1966, 22, 1388.
24 W. Beck, A. Melnikoff, and R. Stahl, Chem. Ber., 1966, 99, 3721.
2 5 A. R. Manning and J. R. Miller, J . Chem. SOC. ( A ) ,1966, 1521.
26 R . W. Cettrall and R. J. H. Clark, J . Organometallic Chem., 1966, 6, 167.
2 7 R. E. Winters and R. W. Kiser, J . Chem. Phys., 1966, 44, 1964.
2 8 B. F. 0. Johmon, J. D. Johnston, J. Lewis, and B. H. Robinson, Chem. Comm.,
1966, 851.
2 s J. Lewis, A. R. Manning, J. R. Miller, and 5. M. Wilson, J . Chem. SOC. ( A ) ,1966,
1663.
R. B. King, J . Amer. Chem. SOC.,1966, 88, 2075.
s1 B. F. G. Johnson, J. Lewis, and I. G. Williams, Chem. Comm., 1966, 391.
8 a D. W. Slocum, R. Lewis, and G. J. Mains, Chem. and I n d . , 1966, 2095.
8 a H. Werner and R. Prinz, Chem. Ber., 1966, 99, 3582; J . Organometallic Chem.,
1966, 5, 79; H. Werner, ibid., p. 100.
8 4 R. J. Angelici and J. R. Graham, J . Amer. Chem. SOC., 1966,88, 3658.
85 H. G. Schuster-Woldan,and F. Basolo, J . Amer. Chem. SOC.,1966, 88, 1657.
8 6 L. R. Kangas, R. F. Heck, P. M. Henry, 5. Breitschaft, E. M. Thorateinson, and
F. Basolo, J . Amer. Chem. Soc., 1966, 88, 2334.
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K O H L A N D L E W I S : TRANSITION-METAL C A R B O N Y L S 211
Fe,(CO), system is replaced by an Fe(CO), The structure of a
related triphenylphosphine derivative, [Pe,( CO),1PPh,],39 has also been
determined; one of the terminal carbonyl groups of the E’e2(C0)gunit ia
subktituted by the phosphine. The two bridging carbonyl groups arc

asymetrically bonded to the two iron atoms with iron-carbon distances of
1.74 and 1.98A.. The structure of the hexapyridineiron salt of the ion
[Fe,(C0),,]2- has been determined by X-ray analysis; an Fe(CO), unit is
co-ordinated to a basal Fe,(CO), fragment with the remaining carbonyl
group bridging the three irons of the E”e,(CO)ggroup.4o The structure of
the tetracobalt dodecacarbonyl has been shown to involve the co-ordination
of a Co(CO), group to a plane of cO,(Co)g in which three of the carbonyl
groups are bridging the three cobalt atoms in pairs.37 The corresponding
iridium compound was found to have no bridging carbonyl groups, whilst
the infrared spectra indicate that the corresponding rhodium complex has a
similar structure to the cobalt complex.41 Baird and Wilkinson p2 have
shown that the sulphur analogue of carbonyl complexes may be obtained
from the reaction of carbon disulphide with rhodium and ruthenium
salts, e.g.,
cs, c1,
(Ph,P),Rh(CO)Cl+ (Ph,P),Rh(CS)Cl+ (Ph,P),Rh(CS)Cl,.
The X-ray structure of the rhodium@) complex indicates a linear
rhodium-carbon-sulphur I n contrast, tetrakistriphenylphosphine-
platinum(0) reacts with carbon disulphide to give an addition complex
(Ph,P),PtCS, in which the platinum is considered to bond to the carbon
and one of the sulphur atoms.44
Carbonyls and Carbonyl Halides.-A new low-pressure synthesis of ruth-
enium carbonyl from ruthenium chloride with zinc in methyl alcohol under a
CO pressure of less than 100 atmosphere is given.45 The reactivity of this
carbonyl with phosphines, nitric oxide, and organic dienes has been investi-
gated.4* With phosphines and dienes, trinuclear metal clusters occur in
the products, whilst in nitric oxide the dinitrosyldicarbonylruthenium is
formed. A range of technetium carbonyl adducts has been prepared with
phosphines, thiols, and halides as co-ordinated groups.47 Manganese penta-
carbonyl-nitrate has been shown to react with pyridine and bipyridyl to
give tricarbonyl adducts in which the nitrate group is still co-ordinated to
the metaL4* Anionic halogeno-rhenium carbonyl complexes have been pre-
pared and both mononuclear and binuclear systems have been isolated.49
s7 C. H. We; and L. F. Dahl, J . Amer. Chem. SOC.,1966, 88,1821.
D. J. Dahm and R. A. Jacobson, Chem. Comrn., 1966, 496.
89 R. J. Angelici and E. E. Siefert, Inorg. Chem., 1966, 5, 1457.
4 0 R. J. Doedens and L. F. Dahl, J. Amer. Chem. SOC., 1966, 88, 4847.
41 W. Beck and K. Lottes, Chem. Ber., 1961, 94, 2578.
42 M. C. Baird and G. Wilkinson, Chem. Cornm., 1966, 267.
43 J. L. De Boer, D. Rogers, A. C. Skapski, and P. G. H. Troughton, Chem. Comm.,
1966, 756.
4 4 M. C. Baird and G . Wilkinson, Chem. Comm., 1966, 514.
4 6 M. I. Bruce, F. G. A. Stone, Chem. Cormn., 1966, 684.
J. P. Candlin, K. K. Joshi, and D. T. Thomson, Chem. and Id., 1966, 1960.
W. Hieber, F. Lux, and C. Herget, 2. Nuturforsch., 1965, 20b, 1159.
4 8 C. C. Addison and M. Kilner, J . Chem. SOC., ( A ) 1966, 1249.
4 9 E. W. Abel, I. S. Butter, M. C. Ganorkar, C. R. Jenkins, and M. H. B. Stiddard,
Inorg. Chem., 1966, 5, 25.
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The reaction of carbon monoxide with hexachlororuthenate-(n) and -(m)
yields a variety of anionic ruthenium carbonyl-halide derivatives.50 The
formation of [Ru(CO)(H,O)C1J2- from ruthenium chloride and formic acid
has been studied k i n e t i ~ a l l y . ~The

~ synthesis of the Rh(r) and Rh(m)
complexes trans-[RhX(CO)L,] (X = C1, Br, I, SCN; L = PR,, AsR,) and
[Rh(CO)L,X,] (X = C1, Br; L = PR,) is reported. The rhodium(1) com-
pounds react with Ph2PCH,CH2PPh2(diphos) to give the very stable salt
Rh(diphos),Cl. 52 The corresponding cobalt complex is obtained from
the interaction of [Co(diphos),] and Co(diphos),X2,5S whilst the iridium
analogue is prepared from either the dicarbonyl-amine-halide complexes,
(CO),(amine)IrCl, with ph~sphine,~* or by the equivalent reaction used for
the rhodium salt.54 In the latter case the presence of a carbonyl inter-
mediate [Ir(diphos),(CO)]Cl has been detected. This compound may also
be prepared from the salt [Ir(diphos),]Cl with carbon monoxide.64 The
iridium salt reacts with oxygen to form [O,Ir(diphos),]Cl, and forms six-
co-ordinate adducts with H,, HCl, HBr, H,S, and halogens, whilst five-
co-ordinate adducts are formed with SO, and 54 Oxidative addition
reactions of this type have been extensively reported for the iridium and
rhodium d8 systems of the type [L,M(CO)X] (L = phosphine; X = halogen),
to give L,M(CO)X,YZ (M = Rh; YZ = CH,COBr) 5 2 (M = f r ; YZ = HF,
HC1, HBr, HI, H2S,55RS02C1).56 The iridium(=) X-sulphinates
[( Ph,P),( CO)Cl,Ir(SO,R)], formed by this last reagent, lose sulphur dioxide
if R = p-tolyl or phenyl, to give the aryl-iridium complex [L,Ir(CO)C1,R].56
With boron trihalides 57 for rhodium and sulphur dioxide 5 8 with iridium,
five-co-ordinate complexes are formed. The X-ray structure of the latter
compound [(Ph,P),Ir(CO)Cl(SO,)] has been determined and shows a tetra-
gonal bipyrimidal stereochemistry with bonding of the sulphur dioxide
through the s~lphur.5~ Tetracyanoethylene forms addition complexes with
both the rhodium and iridium series as also with the corresponding rhodium
thiocarbonyls [Rh(Ph,P),(CS)X] (X = Cl,Br); direct bonding of the olefin
group is postulated t o occur in these complexes.g0 A kinetic study of the
addition of oxygen, hydrogen, and methyl iodide to the series trans-
IrX(CO)(PPh,), (X = Cl, Br, I) establishes that the reaction of hydrogen
and oxygen is similar and differs from that of methyl iodide.61 The re-
markable nitrogen complex [(Ph,P),Ir(N,)Cl] is formed by the reaction
of the complex [Ir(CO)Cl(PPh,),] with a number of acid azides; a band a t
2095 cm.-l in the infrared spectrum is associated with the nitrogen-nitrogen
J. Halpern, B. R. James, and A. L. W. Kemp, J . Amer. Chem. SOC.,1966, 88,
6142.
s1 J. Halpern and A. L. W. Kemp, J . Amer. Chem. SOC.,1966, 88, 5147.
52 J. Chatt and B. L. Shaw, J. Chem. SOC.( A ) ,1966, 1437.
63 A. Sacco, M. Rossi, and C. F. Nobile, Chem. Comm., 1966, 589.
6 * L. Vaskrt and D. L. Catone, J . Amer. Chem. SOC.,1966,88, 5324; W. Hisber and
V. Frey, Chem. Ber., 1966, 99, 2607.
1966, 88, 6325.
6 s L. Vaska, J . Amer. Chem. SOC.,
s6 J. P. Collman and W. R. Roper, J. Amer. Chem. SOC.,1966, 88, 180.
57 P. Powell and H. Noth, C h m . Comm., 1966, 637.
18 L.Vaska and S. S. Bath, J . Amer. Chem. SOC.,1966, 88, 1333.
6 9 S. J. Laplaca and J. A. Ibers, Inorg. Chem, 1966, 5, 405.
60 W. H. Baddley, J . Amer. Chem. SOC.,1966,88, 4546.
61 P. B. Chock and J. Halpern, J. Amer. Chem. SOC.,1966,88, 9511.
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K O H L A N D LEWIS : T R A N S I T I O N - M E T A L C A R B O N Y L S 213
stretching frequency.62 This complex is related to the nitrogen adducts
[(N,)Ru(NH,),]X, reported by Allen and Sen~ff,~, the X-ray structure of
which establishes a linear metal-nitrogen grouping.6 4 A polymeric carbonyl
halide of palladium, [PdCl(CO)],, has been obtained by passing moist air

through a suspension of PdC1,CO. The complex is a red-violet solid which is
insoluble in organic solvents.65
Nitrogen and Phosphorus Derivatives.-The synthetic use of tris(aceto-
nitrile)tungsten tricarbonyl has been developed, and yields, with benzene,
toluene, p-xylene, mesitylene, cyclohepta-1,3,5-triene, cyclo-octadiene,
dimethylaminofulvene, the tricarbonyl adducts, whilst tetracarbonyl com-
plexes are formed with norbornadiene and cyclo-octa-l,5-diene, and a
dicarbonyl complex with cyclohexa-1,3-diene,W(CO),(C6H,),.66 The photo-
chemical production of pentacarbonyl amine complexes of the Group VI
carbonyls has been reported.67 Reactions of amines with molybdenum
pentacarbonyl-halogen anions, [Mo(CO),X]-, yield, in addition to the penta-
carbonyl amine complexes, the tetracarbonylbis(amine) adducts, the relative
proportions produced depending upon the halide anion involved.68 The
tetraethylammonium salts of the halogenopentacarbonyl anions of the
Group V I metals give mono-, bis-, and tris-isonitrile derivatives on reaction
with both alkyl and aryl i~onitriles.6~Mixed phosphine or amine-bipyridyl
or o-phenanthroline complexes of the form M(CO),X,Y and M(CO),X2Y,
[M = Cr, Mo; W, X, = phen, bipy; Y = py, NH,, Ph,P, (RO),P] have
been reported.'O Potassium cyanide reacts with the (dicarbonyl)bis(bipyidyl)
complexes of chromium, molybdenum, and tungsten with displacement of
the nitrogen bonds, to give the salts K4[M(C0)2(CN)4] (M = Cr, Mo, W).'l
Octamethyltetraphosphonitrile reacts with molybdenum carbonyl to give a
fetracarbonyl phosphonitrile complex. The phosphonitrile is considered t o
bond to the molybdenum through the two nitrogens at opposite ends of the
molecule.71a
It has been suggested that succinonitrile bonds to manganese by a
n-interaction of the cyano groups in the complexes Mn(CO),(NCCH,CH,CN)X
(X = C1, Br, I),72 whilst a normal a-bonding structure of the cyanide is
considered to occur in the acrylonitrile dimer, [(CO),Fe(CH, = CHCN)],.
The co-ordination number of the iron is attained by co-ordination of the
olefin group, the acrylonitrile acting as a bridging group between the two
metal ions.73 Nickel carbonyl reacts with diallylcyanamide to give the
dimer [( R,N*CN),Ni(CO)], ; the structure is considered to involve bridging
62 J. P. Collman and J. W. Kang, J. Amer. Chem. SOC.,1966, 88, 3459.
63 A. D. Allen and C. V. Senoff,Chem. Comm., 1965, 621.
6 4 F. Bottomley and S. C. Nyberg, Chem. Comm., 1966, 897.
6 5 A. Treiber, Tetrahedron Letters, 1966, 2831.
* 6 R. B. King and A. Fronzaglia, Inorg. Chem., 1966, 5, 1837.
6 7 W. Strohmeier, J. F. Guttenberger, H. Blumenthal, and G. Albert, Chern. Ber.,
1966, 99, 3419.
6 8 H. D. Murdoch and R. Henzi, J . Organometallic Chem., 1966, 5, 463.
69 H. D. Murdoch and R. Henzi, J . Organometallic Chem., 1966, 5, 166.
7 0 L. W. Houk and G. R. Dobson, Inorg. Chem., 1966, 5, 2119.
71 H. Behrens, E. Lindner, and J. Rosenfelder, Chem. Ber., 1966, 99, 2744.
'la J. Dyson and N. L. Paddock, Chem. Cmm., 1966, 191.
12 M. F. Farona and N. J. Bremer, J . Amer. Chem. SOC., 1966, 88, 3735.
7 s E. H. Schubert and R. K. Sheline, Inorg. Chem., 1966,5, 1071.
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carbonyl groups with the two nitrogens bonding and the diallylcyanamide
acting as chelate.74 1,4-Diazabuta-l73-dienecarbonyl complexes of nickel
and molybdenum have been obtained, and the reaction of these with iodine
and triphenylphosphine rep0rted.7~ The interaction of a series of new

phosphine ligands with metal carbonyls has been reported recently.
Tetrakis(diphenylphosphinomethy1)methane reacts as a double bidentate
ligand with chromium, molybdenum, tungsten, and nickel carbonyls, to yield
the spirocyclic compounds M(GO),(Ph,P*CH,), and C(CH,P.Ph,),M( CO),
(M = Cr, Mo, W, n = 4;76Ni, n = 2 77). The nitrogen-phosphorus mixed
ligands Ph,PC,H,NEt,(NP), PhP(C,H,NEt,),(NPN), and
(Ph,PC,H,),NEt(PNP) react with molybdenum carbonyl to yield
Mo(CO),NP, Mo(CO),(NPN),and Mo(CO),(PNP),78respectively, whilst the
potentially quadridentate group tris-(o-diphenylphosphinopheny1)phosphine
(QP) reacts with manganese carbonyl compounds to give complexes in
which the ligand is bidentate, [MnX(CO),(QP)](X = halogen), terdentate,
[Mn(CO),QP]+, or quadridentate, [Mn(CO),QP] +. The related ligands bis-
(o-dipheny1phosphino)phenylphosphine(TP) and o-phenylenebisdiphenyl-
phosphine (DP) yield the complexes [Mn(CO),TP]+ and [Mix( CO),DP].'@
Oxidation of [Mn(CO),(diphos),]Clwith a range of oxidising agents yields
the paramagnetic manganese(=) ion [Mn(CO),(diphos),]2+.
The first phosphine complexes of osmium carbonyl, Os(CO),(PPh,),, have
been isolated from the reaction of OsX,(CO),(PPh,), (X = halogen) with
zinc in the presence of CO. The carbonyl-phosphine complex reacts with
halogens to give the ions [Os(CO),(PPh,),X]+ (X = Br, I) and hydrogen
chloride to give [0s(CO),(C1,)(PPh3),].~~ The preparation of cationic car-
bony1 complexes, using the method of Fischer, Fichtel, and Oefele,82 has
been applied to rhodium and iridium carbonyl phosphine and stibene com-
plexes, to yield the ions [M(CO),L,]+ [M = Rh, I r ; L = PPh,, P(C,H,J,,
SbPh,].g3 With antimony, the hydrides HM(CO)(SbPh,),Cl, (M = Rh, Ir)
were also isolated.
A series of phosphine-substituted products of nickel carbonyl with the
ligand 2,8,9-trioxa-l-phospha-adamantane, P(OCH,),(CH,),, have been
obtained. They are of the general formulae Ni(CO),-,L, (x = 1,2,3,4).
With iron, chromium, molybdenum, and tungsten, the corresponding mono-
and di-substituted compounds were obtained. The reactions of nickel
carbonyl with the series of bifunctional phosphines (CF,)2POP(CF,)2,
(CF,),PSP(CF,),, and (CF,),PN(Me)P(CP3), lead to polymers involving
bridging carbonyl groups.s5
74 H. Bock and H. tom Dieck, Chem. Ber., 1966, 99, 213.
75 H. Bock and H. tom Dieck, Angew. Chem., 1966, 78, 549.
7 6 J. Ellermann and K. Dorn, J . Organometallic Chem., 1966, 6, 157.
7 7 J. Ellermann and K. Dorn, Angew. Chem., 1966, 78, 547.
7 8 G. R. Dobson, R. Craig Taylor, and T. D. Walsh, Chem. Comm., 1966, 281.
7 9 B. Chiswell and L. M. Venanzi, J . Chem. SOC.( A ) ,1966, 417.
8 0 M. R. Snow and M. H. B. Stiddard, J . Chem. SOC. ( A ) ,1966, 777.
81 J. P. Collman and W. R. Roper, J . Amer. Chem. SOC.,1966, 88, 3504.
8a E. 0. Fischer, K. Fichtel, and K. Ofele, Chem. Ber., 1962, 95, 249.
83 W. Hieber and V. Frey, Chem. Ber., 1966, 99, 2614.
8 4 D. G. Hendricker, R. E. McCarley, R. W. King, and S. G . Verkade, Inorg. Chem.,
1966, 5, 639.
1966, 88, 5354.
8 6 A. B. Burg and R. A. Sinclair, J . Amer. Chem. SOC.,
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K O H L A N D LEWIS : TRANSITION-METAL CARBONYLS 215
Sulphur Derivatives.-The interaction of molybdenum and tungsten car-
bonyls with nickel bis(dithioketone) yields the a-dithioketone complexes
M(S,C,R,)(CO), (M = W, R = Me) and M(S,C,R,),(CO), (M = Mo, W,
R = alkyl or aryl); the reactivity of the carbonyl groups in these molecules

to phosphine molecules has been investigated.86 The investigation of the
reactions of thiols with rhenium and manganese carbonyl complexes has
continued,*', 88 and the field has been extended with the formation of the
corresponding selenium ad duct^.^^
A series of manganese carbonyl derivatives of dithiocarbonates and
monothiocarbonates has been reported 00'-dimethyl and -diphenyl
dithiophosphate complexes of manganese carbonyl have been studied, and
in the bipyridyl complexes Mn(CO),( bipy)(S,P(OR), the ligand appears to
be acting as a unidentate rather than a bidentate g r o ~ p . ~The
l product of
the reaction of bis(trifluoromethy1)dithietin with the cobalt carbonyl has
been established to be trimeric [C,F,S,Co(CO)], from the mass spectra.
The complex is paramagnetic (p = 1-84B.M.) as anticipated on this formula-
tion. The isoelectronic nitrosyl iron compound has also been shown to be
trimeric from the mass spectra, [E"e(NO)C,F6S,],.92
Miscellaneous.-The preparation of compounds with boron-manganese
bonds has been rep0rted.~3 Bisdimethylaminoboron chloride reacts with
sodium manganesepentacarbonylto give the compound (Me,N),B-lSh(CO),.
The complex reacts with hydrogen a t 100 atmospheres to give manganese
carbonyl and bis(dimethylamino)borane, and with bromine to yield bis-
(dimethy1amino)boronbromide and pentacarbonylmanganesebromide. The
IIB n.m.r. spectra are interpreted. as indicating back-donation from the
manganese d-orbitals to the trigonal planar boron atom. A series of tri-
phenylphosphine oxide and bipyridyl dioxide complexes of rhenium carbonyl
halides is reported.94
Hydrides.-The formation of bis-(n-cyclopentadieny1)zirconiumdihydride
and the monohydride-borohydride adduct is reported to occur by
action of trimethylamine on the corresponding borohydride complex
(n-C,H,),Zr(BH,),. The complexes are postulated to have a polymeric
bridging hydride structure S 5 with the metal-hydrogen vibration occurring
at 1540 cm.-l. The reaction of nitrogen with transition-metal complexes
to give ammonia has been establi~hed.~6For the system
(n-C,H,),TiCl,-C,H,MgX, the e.s.r. spectra have been interpreted as indi-
8 6 G. N. Schrauzer, V. P. Mayweg, and W. Heinrich, J . Amer. O h m . Soc., 1966,
88,5174; G. N. Schrauzer, V. P. Mayweg, H. W. Finck, and W. Heinrich, ibid., p. 4604.
8 7 A. G. Osborne and F. G. A. Stone, J . Chem. SOC.( A ) , 1966, 1143.
8 8 E. W. Abel and B. C. Crosse, J . Chern. SOC.( A ) ,1966, 1141.
8 g E. W. Abel, B. C. Crosse, and G. V. Hutson, Chem. and Id., 1966,238.
g o W. Hieber and M. Gscheidmejer, Chem. Ber., 1966, 99, 2312.
O 1 F. A. Hartman and A. Wojcicki, Inorg. Nuclear Chem. Lettes, 1966, 2, 303;
R. L.Lambert and F. A. Manuel, Inorg. Chem., 1966,5, 1287.
g 2 R. B. King and F. T. Korenowski, Chem. Comm., 1966, 771.
CJ* H. Noth and G . Schmid, J . Organometallic Chem., 1966, 5, 109.
O 4 U. Sartorelli, F. Canziani, and F. Zingales, Inorg. Chem., 1966, 5, 2233.
96 B. D. James, R. K. Nanda, and M. G. H. Wallbridge, Chem. C m . , 1966, 849.
CJ6 M. E. Vol'pin and V. B. Shur, Nature, 1966,209,1236; M. E. Vol'pin, V. B. Shur,
K. N. Latyaeva, L. J. Vyshinskays, A. L. Shul'gaitser, Izvest. Akad. Nauk S.S.S.R.
Ser. khim., 1966, 385.
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cating the presence of binuclear hydride bridges with nitrogen insertion
into those hydride bonds with formation of imine specie^.^'
The wide-line n.m.r. spectrum of the manganese pentacarbonyl hydride
indicates that the H-Mn bond distance is 1*28A, and hence establishes
the presence of “ short ” metal-hydrogen bonds in these sy~tems.~g
The preparation and reactions of hydridot etracarbon yltriphenylphosphine-
manganese(@ has also been reported.99 The X-ray structures of the
ion [Cr,H(CO),,]- have been interpreted in favour of a linear Cr-H-Cr
group.100 The synthesis of [M,H(CO),,]- and [M2(CO),o]2-(M = Cr, Mo,
and W), and the intercorrelation between the two sets of ions, has been
established ; the formation of mixed complexes [MM’H(CO),,]- has been
detected from the n.m.r. spectra, and the infrared and 11.111.13. data on the
series interpreted in terms of a symmetrical hydrogen-metal bridge.101 The
addition of the Lewis acids BF, and BCI, to bis mcyclopentadienyl hydrides
of molybdenum, tungsten, and rhenium leads to the formation of 1 : 1
adducts.lo2 A new polynuclear hydride of rhenium HRe,(CO),, has been
reported lo1 and the exchange of 13C0 with the hydride studied; this
enables the preparation of stereospecific 13C0 labelled Re,(CO),, to be
obtained.lo1 A comprehensive study of the rhenium hydride phosphine
system has been carried and yields three classes of compounds,
ReH,(PR,),, [ReHz(PR3)2]n,and [ReH,(PR,),]. A nitrosyl hydride of
iron HFe(NO)(PF,), has been obtained by acidification of the potassium
salt prepared by the action of potassium amalgam on the dinitrosylbis-
trifluorophosphineiron complex.lo4
Three new ruthenium hydrocarbonyls have been obtained, H,Ru,(CO),,
and H2Ru,(C0),,.28, lo5 The first compound appears to exist in two different
forms, as the proton n.m.r. signals occur at z 18.5 and 23.5 for the two
isomers. The hydrogen-metal stretching vibration in some iridium and
osmium carbonyl hydridophosphine complexes have been shown to be
coupled to the carbonyl vibration when the hydrogen is trans to the carbonyl,
but no interaction occurs in the cis-compounds.lo6 Some hydrido-complexes
of iridium(@ with trichlorotin and a variety of phosphine ligands have been
reported. 107 The first pure hydrido-complexes with only non-n-bonding
ligands co-ordinated to the metal have been obtained by the zinc-dust
reduction of chloropenta-amminerhodium(m) salts,1°8 in the anions
[RhH(NH,),]2+ and [RhH(H20)(NH,)J2+. A related cyanide complex,
K,[RhH(CN),(H,O)], has been obtained from rhodium carbonyl chloride
07 H. Brintzinger, J . Amer. Chem. SOC.,1966, 88, 4305, 4307.
98 T. C. Farrar, W. Ryan, A. Davison, and J. W. Faller, J . Amer. Chem. SOC.,1966,
88, 184.
99 B. L. Booth and R . N. Haszeldine, J . Chem. SOC.( A ) ,1966, 157.
100 L. B. Handy and P. M. Treichel, J . Amer. Chem. SOC.,1966, 88, 366.
101 R. G. Hayter, J . Amer. Chem.SOC., 1966,88,4376; R. W. Hamil and H. D . Kaesz,
Inorg. Nuclear Chem. Letters, 1966, 2, 69; W. Fellmann and H. D. Kaesz, ibid., p. 63.
102 M. P. Johnson and D. F. Shriver, J . Amer. Chem. SOC.,1966, 88, 301.
lo3 J. Chatt and R. S. Coffey, Chem. Comm., 1966, 545.
lo4Th. Kruckand W. Lang, Chem. Ber., 1966, 99, 3794.
1 0 5 J. W. S. Jamieson, J. V. Kingston, and G. Wilkinson, Chem. Cmm., 1966, 569.
L. Vaska, Chem. Comm., 1966; J . Amer. Chem. SOC.,1966,88,4100.
1 0 7 R. C. Taylor, J . F. Young, and G. Wilkinson, Inorg. C h . , 1966,5, 20; A. Sacco,
R. Ugo, and A. Moles, J . Chem. SOC.( A ) ,1966, 1670.
168 J. A. Osborn, A. R. Powell, and G . Wilkinson, Chem. Comm., 1966, 461.
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and cyanide ; the compound reacts with nitric oxide, tetrafluoroethylene,
and oxygen to give K,[Rh(CN),(NO,)H,O], K3[Rh(CN)5C2F4H],and
K4[(CN),(H20)Rh0,Rh(CN),( H,O)], respectively.lo9
A series of equilibria l10 have been established between zerovalent

platinum phosphine complexes and hydrido-phosphinecomplexes on reaction
of the tetrakistriphenylphosphineplatinum(0)and tristriphenylphosphine-
platinum(0) complexes with acids (L = triphenylphosphine).
-L HC1 -L
PtL, PtL, \ k [ P t H L , ] C l [PtHClL,]
+L KOH
+L -TICXI lHCl
Ik
[PtH,C1,L,I
Using 110 this system, it has been possible to isolate a series of derivatives of
the type [PtH(PPh,),]X (X = ClO,-, BF4-, HS04-, CH,0S03-) and
[PtHY(PPh,),] (Y = CN-, SCN-). The reaction of the complex
[PtH(PPh,),]HSO, with base in the presence of oxygen produces the zero-
valent bistriphenylphosphineplatinum compound,lll [Pt(PPh,),]. The bis-
phosphine chlorohydride platinum complex has been shown to react with
tetracyanoethylene to give the first example of a carbon, with a cyanide
group attached, bonding directly to a metal, (Ph,P),Pt(C6N,).ll2
During the past year, continued interest in homogeneous hydrogenation
using transition-metal complexes as catalysts has been maintained. A n
extensive discussion of the kinetics and mechanism of these reactions using
the complexes (Ph,P),RhX (X = C1, Br, I) as catalysts has been given,113
and the activity of the related compounds (MPh,),RhCl (M = As, Sb)
assessed.ll4 Por the system (PtCl,C,H,), it is concluded that hydrogenation
of the n-bonded ethylene occurs without the formation of a-diadsorbed
intermediates.ll5 The homogeneous hydrogenation of aldehydes has been
accomplished under hydroformylation conditions using a rhodium trichloride
catalyst ; rhodium carbonyl compounds are possible intermediates in this
process.lls The kinetics and mechanism of the homogeneous catalytic
hydrogenation of maleic and fumaric acids with a ruthenium(=) chloride
catalyst has been studied. Tracer studies indicate that the hydrogen atoms
added to the olefin group originate from the solvent rather than the hydrogen
gas.ll7
Nitrosyls.-The e.s.r. spectra of the metal pentacyanonitrosyl complexes
of some of the first-row transition elements have been discussed.llg The
infrared spectra of various metal nitrosyl complexes 119have been measured
loB D. N. J.
Lawson, M. Mays, and G. Wilkinson, J. Chem. Soc.
( A ) , 1966, 52.
110 F. Cariati, R. Ugo, and F. Bonati, Inorg. Chem., 1966, 5,
1128.
ll1 R. Ugo, F. Cariati, and G. La Monica, Chem. Comm., 1966, 868.
112 W. H. Baddley and L. M. 5,
Venanzi, Inorg. Chem., 1966, 3 3 .
119 J. A. Osborn, F. H. Jardine, J. F. Young, and G. Wilkinson, J. Chem. SOC.( A ) ,
1966, 1711.
J. T. Mague and G. Wilkinson, J. Chem. SOC.( A ) ,1966, 1736.
115 K. E. Hayes, Nature, 1966, 210, 412.
ll6 B. Heil and L. Mark6, Chem. Ber., 1966, 99, 1086.
11' J. Halpern, J. F. Harrod, and B. R. James, J. Amer. Chem. Soc., 1966, 88, 6150.
P. T. Manoharan and H. B. Gray, Incrg. Chem., 1966, 5, 823; B. A. Goodman,
J. '€3. Raymor, and M. C. R. Symons, J. Chem. SOC.,( A ) 1966, 994.
11* P. Gans, A. Sabatini, and L. Sacconi, Inorg. Chem., 1966, 5, 1877.
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between 4000 and 80 cm.-l. The approximate nitrosyl and carbonyl

force constants have been calculated for the isoelectronic series Mn(NO),CO,
Fe(NO),(CO),, Co(NO)(CO),,and Ni(CO),, and the variation of these values
for the substituted derivatives LMn(NO),, Ni(CO),L,, Fe(NO),L,, and

Co(NO)L, discussed in terms of the n-bonding properties of the group L.120
The presence of considerable n-bonding between nitrogen and chromium in
the complex ~-C,H,Cr(NO),Cl has been deduced from the X-ray structure
of the compound.121 The presence of geometrical isomers of the series
[C5H5Cr(NO)XI2 [X = NMe,, SR; (Y-PeSMe),, Y = (CO),, (NO),],
[C,H,NiX], (X = SMe), and [C,H,Fe(CO)X], (X = SR, PPh,) has been
established,12, and their separation achieved. Nitrosyl-iron and -cobalt
adducts of the ligands [S,C,R,] (R = C,H,, CF,, CN) have been isolated.l23
A series of octahedral nitrosyl ruthenium complexes of the type Ru(NO)X,L,
has been reported (X = halogen; L = pyridine, CH,CN, R,As, R,Sb, R2S,
bipy, phen, diar~ine).12~Both five-co-ordinateand six-co-ordinatebinuclear
complexes (NO)RuI,X, (X = pyridine, bipy, R,As) have been prepared.125
The X-ray structure of the alleged seven-co-ordinate complex
(NO)Ru(S2CNEt,),shows it to be six-co-ordinate, with one of the dithio-
carbonate groups being bonded as a unidentate group.l26 Reaction of the
compounds Co(NO)(CO),and Fe(NO),(CO),with excess of diphos established
the presence of '' long lived " intermediates with the phosphine bonded
through only one phosphorus atom, which react finally to give the disub-
stituted derivatives. The diphosphine has been shown to act as a bridging
group12' between two [Co(NO)(CO),]groups, and on reaction with both
carbonyls forms the mixed complex (NO),Fe(C0)-diphos-Co( CO),(NO).
I n the complex C1(NO),Co-diphos-Co(NO),C1 a similar diphos bridge is
present. Binuclear phosphido-bridged adducts, [(NO),M-PPh,], (M = Fe,
Co) have also been obtained.l28?l Z 9 A series of cyanonitrosyl and cyano-
carbonylnitrosyl anions of cobalt has been prepared from the reaction of
potassium cyanide with nitrosyltricarbonylcobalt in liquid ammonia.130
The kinetics and mechanism of the reactions of a variety of phosphines,
phosphites, arsines, isonitrile, and pyridine derivatives with the complex
[NOCo(CO),] have been elucidated,131 and the products [Co(NO)(CO),L]
is01ated.l~~A large range of mono- and di-nitrosyl complexes of cobalt with
l a o Q.R. van Hecke and W. Dew, I n o r g . Chem., 1966, 5, 1960.
lal 0. L. Carter, A. T. McPhail, and G. A. Sim, J . Chem. SOC. ( A ) ,1966, 1095.
laaM. Ahmad, R. Bruce, and G. Knox, 2. Naturforsch., 1966, 216, 289.
lP8 J. Locke, J. A. McCleverty, E. J. Wharton, and C. J. Winscom, Chem. Comm.,
1966, 677.
l a 4J. Chatt and B. L. Shaw, J . Chem. SOC.,1966, 1811; M. B. Fairy and R. J. Irving,
ibid., p. 475.
mi R. J. Irving and P. G. Laye, J . Chem. SOC.( A ) ,1966, 161.
18* A. Domenicano, A. Vaciago, L. Zambonelli, P. L. Looder, and L. M. Vemmzi,
Chem. C m m . , 1966,476.
la' R. J. Mawby, R. Morris, and E. M. Thorsteinaon, and F. Basolo, Inorg. Chem.,
1966, 5, 27.
1 2 8 W. Hieber and G. Neumair, 2. anorg. Chem., 1966, 342, 93.
lze W. Hieber and R. Kummer, 2.anorg. Chem., 1966, 344, 292.
l9O H. Behrens, E. Lindner, and H. Schindler, Chem. Ber., 1966, 99, 2399.
E. M. Thorsteinson and F. Basolo, J . Amer. Chem. SOC.,1966, 88, 3929.
ls4 E. M. Thorsteinson and F. Basolo, Inorg. Chern., 1966, 5, 1691.
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K O H L A N D LEWIS: TRANSITION-METAL CARBONYLS 219
ethylenediamine, pyridine, and aniline as ligands has been e ~ t a b l i s h e d , l ~ ~ - l ~ ~
and the nature of the nitrosyl group in theredand black penta-ammine cobalt
salts discussed.135
Transition-metal Carbonyl Complexes containing Metal-Metal Bonds.-

An electrochemical study of a large range of compounds containing
metal-metal bonds has been reported, and the nucleophilicities of some
transition-metal complex anions studied.136 The metal-metal bond energy
in manganese decacarbonyl has been determined 137 t o be 18.9 & 1.4 kcal.
from mass-spectral data; this value falls near the range 34 & 13 kcal.
determined earlier.138 Raman spectroscopy has been applied to some
binuclear metal carbonyl complexes, and shows that the approximate
force constants of the decacarbonyls M2(C0)10 follow the order
Re-Mn > R e R e > Mn-Mn.139 The infrared spectra of manganese deca-
carbonyl and the bisphosphine substituted complexes l4O9 141 have been
discussed in terms of the Cotton-Kraihanzelm0de1.~4~The data imply that
there is no n-bonding across the metal-metal bond.l4l The triphenyl-
phosphine-manganese decacarbonyl system has been reinvestigated, and the
adducts isolated are (Ph,P)Mn,(CO), and [(Ph,P)Mn(CO),],. The presence
of a monomeric paramagnetic species, [(Ph,P)Mn(CO),], has been refuted.143
However, the kinetics of the reaction of Ph,P with iodine and manganese
decacarbonyl indicate that the primary step is fission of the metal-metal
bond to give Mn(CO), radicals.ld4 The kinetics of carbon monoxide exchange
of a variety of carbonyls containing Hg-Co, Cd-Co, Sn-Coy Au-Coy and
Au-Mn bonds have been carried and the rate of exchange is found t o
vary widely. Anisotropic electron-transport has been established in single
crystals of the complexes Ir(acac)(CO), and Rh(aca~)(CO)~ (acac = acetyl-
acetonate ion). Maximum electrical conductivity occurs along the axes of
the metal-metal bonds.l*6
The structure of the compound (C,H5C,C6H,)Fe,(CO)ginvolves a triangle
of iron atoms each with three terminal carbonyl groups. The organic group
is situated above this plane with one of the acetylenic carbon atoms bonded
to all the iron atoms, whilst the other acetylene carbon is bonded to only
two of the iron atoms.147 A new osmium dodecacnrbonyl complex, with
133 W. Beck, W. Hieber, and G. Neumair, 2.anorg. Chem., 1966, 344, 285.
13p T. B. Jackson, M. J. Baker, J. 0. Edward, and D. Tutas, Inorg. Chern., 1966,
88, 2046.
136 J. B. Raynor, J . Chem. SOC. ( A ) , 1966, 997.
13$ R. E. Dessy, P. M. Weissman, and R. L. Pohl, J . Amer. Chem. SOC.,1966, 88,
5117; R. E. Dessy, R. B. King, and M. Waldrop, ibid., p. 5112; R . E. Dessy, F. E.
Stary, R. B. King, and M. Waldrop, ibid., p. 471.
137 D. R. Bidinosti and N. S . McIntyre, Chem. Comm., 1966, 555.
13* F. A. Cotton and R . R. Monchamp, J . Chem. Soc., 1960, 533.
l B D H. M. Gager, J. Lewis, and M. J. Ware, Chem. Comm., 1966, 616.
14* D. J. Parker and M. H. B. Stiddard, J . Chem. Soc., 1966, 695.
141 J. Lewis, A. R. Manning, and J. R. Miller, J . Chem. SOC.( A ) ,1966, 845.
I r a F. A. Cotton and C. S . Kraihanzel, J . Amer. Chem. SOC.,1962, 84, 4432.
l r 3 H. Wawersik and F. Basolo, Chem. Comm., 1966, 366.
144 D. Hopgood, and A. J. Po6, Chem. Cmnm., 1966, 831.
145 S. Breitschaft and F. B ~ o l oJ., Amcr. Chent. SOC.,1966, 88, 2702.
146 C. G. P ilt,L. K. Monteith, L. F. Ballard, J. P. Collman, J. C. Morrow, W. R.
Roper, and D. Ulkii, J. Amer. Chem. Soc., 1966, 88,4236.
14' J. F. Blount, L. F. Dahl, C. Hoogzand, and W. Hiibel, J . Amer. Chem. SOP.,
1966, 88, 292.
xi
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osmium tetroxide is reported, OS,(CO)~~,OSO~, and is considered to involve

bonding of the OsO, group through three oxygens to the plane of osmium
atoms.148 A silicon analogue of the dimer [Co,(CO),C], has been prepared
by the reaction of tetraphenylsilane with cobalt carbonyl, and is the f i s t

.
cazbonyl reported 149 with a silicon-silicon bond, [Co,(CO),Si], The prepara-
tion of the complex [Co(CO),],C .CH2CH2C0,H is reported.l5* The X-ray
structure of bis(tricoba1t enneacarbonyl)acetone, obtained by heating the
compound [Co(CO),],CBr to 90°c, shows that insertion of a carbonyl group
between the two carbon atoms of the dimers to give
is involved.151 The interaction of 3,3,3-trifluoropropynewith cobalt carbonyl

has been investigated,162 and the complexes [Co(CO)3],C*CH2CF, (I),
[Co(CO),],HC*C*CF,(11),and [Co(CO),],[HC*C*CF,], (111)have been isolated.
Compound (I) is considered to be a derivative of the [Co,(CO),C] cluster;
(11) is related to the corresponding complex of hexafluorobut-2yne
[(cF,c=cc~,)co,(co)6],153 whilst (111) is postulated to have bridging
o l e h groups. The preparation of a new type of metal cluster with manganese
and iron carbonyls has been reported in the ion [MIIF~,(CO)~,]-,~~~ and the
compound [Mn,Fe(CO)l,] . l S 5 The crystal structure of the complex
n-C,H,Fe(CO),Mn(CO), has been determined and shows that the molecule
contains a metal-metal bond.156 The preparation of the mixed carbonyls
(CO),Re-Mn(CO),, (CO),Re-Co(CO),, and some derivatives has been effected
by a Wurtz-type reaction between anionic and cationic carbonyl species.l5'
A bidentate gold ligand, Ph,P*AuC,H4C6H4Au*PPh2, has been used to pre-
pare the first chelate complex containing metal-metal bonds, by interaction
of the ligand with the anion l?e(CO),2-.158 Cationic complexes in which
mercury is bonded to iron,lS9ruthenium, and osmium l60 carbonyl phosphine
derivatives have been reported. For the iron complex, the stability of the
product depends upon the nature of the phosphine. For ruthenium and
osmium the compounds are formulated as [( CO),M L,(HgX)][HgX,],
(L = Ph,P, X = C1, Br, I; M = Ru, 0s). Substitution reactions of the
compounds (XHg),Fe(CO), (X = CJ, Br), with a variety of nitrogen bases
have been studied.161 The interaction of mercuric chloride with cyclo-
14* B.F.G.Johnson, J. Lewis, I. 0. Williams, and J. Wilson, C h m . Comm., 1966,
391.
149 S. F. A. Kettle and I. A. Khan, J . Organometallic Chenz., 1966, 5, 588; M. G. Bor,
L. Marko, and B. Marko, Chem. Ber., 1962, 95, 333.
150 G. Albanesi and E. Garezotti, Chimica e Industria, 1965, 47, 1322.
151 G.Allegra, E.M. Peronaci, and R. Ercoli, Chem. Comm., 1966, 549.
152 D. A. Harbourne, D. T. Rosevear, and F. 0. A. Stone, Inorg. N w b a r Chem.
LettersI, 1966, 2, 247.
153 J. L.Boston, D. W. A. Sharp, and G. Wilkinson, J . Chem. SOC., 1962, 3488.
154 U. Anders and W. A. G . Graham, Chem. Comm., 1966, 291.
156 E. H. Schubert and R. K. Sheline, 2. Naturforsch., 1965, 206, 1366.
158 P. J. Hansen and R. A. Jacobson, J . 0,rganometallic Chem., 1966, 6, 389.
157 Th. Kruck, M. Hofler, and M. Noack, Chem. Ber., 1966, 99, 1153.
158 B. Chiswell and L. M. Venanzi, J . Chem. SOC. ( A ) ,1966, 901.
159 D. M. Adam, D. J. Cook, and R . D. W. Kemmit, Chem. Comm., 1966, 103.
160 J. P. Co1lma.n and W. R. Roper, C h .Comm., 1966, 244.
16 1 J. Lewis and S . B. Wild, J . Chem. SOC.
( A ) ,1966, 69.
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KOHL A N D L E W I S : T R A N S I T I O N - M E T A L C A R B O N Y L S 221
pentadienylcobalt dicarbonyl162 yields the ionic complex
[Co(CO),(C,H,)HgCl]Cl related to the phosphine carbonyl derivatives of
osmium and ruthenium discussed above.
A wide range of tin-metal bonds has been prepared. A new preparative

technique for the interaction of amido-tin complexes with transition-metal
hydrides has been developed, and leads to the complexes (Ph,P),PtCl(SnMe,)
and (C,H,) (CO),W-SnMe,. A molybdenum-titanium complex,
C,H,(CO),Mo*Ti(OPri),, has been obtained using the same type of r e a ~ t i 0 n . l ~ ~
The reaction of the anions [M(C,H,)(CO),]- (M = Cr, Mo, W) with the com-
pounds R,MX (M = Ge, Sn, Pb; R = Me, Ph; X = halide) yields the
complexes [C,H,( C0),M-M'R3]. The stability of these clusters increases
from chromium to tungsten.16, The preparation and spectroscopic pro-
perties of the series Ph,M'-M(CO), (M' = Si, Ge, Sn, Pb; M = M i , Re) and
X,Sn-M(CO), (M = Re, Mn, X = Me, C1, Br) have been investigated. It
is concluded that in these compounds the Br,Sn- and C1,Sn- groups are
strong n-acceptor ligands.l 6 5 The X-ray structure of the compound
Ph,Sn-Mn(CO), is reported.lG6 The reaction of iron pentacarbonyl with
tributyltin chloride yields the compounds [BuaSnFe(C0),],Fe(CO),,
Bu,Sn,[Fe(CO),],, and Sn[Fe(CO)J,; the last compound may be obtained
directly from stannous chloride and iron carbonyl. The X-ray structure
of this compound indicates a tetrahedral array of iron atoms around the tin,
each iron having four terminal carbonyl groups and the iron atoms being
bonded to each other in pairs.167 The preparation and infrared spectra of
the complex RSn[Co(CO),], (R = Ph, Me, CH, = CH, n-C4H5, C1, Br, I)
have been reported.16s Interaction of rhodium and iridium carbonyl phos-
phines, [L,M(CO),], with sodium amalgam in the presence of carbon monoxide
and subsequent addition of trimethyltin halide, triphenylphosphinegold
halide, or mercuric cyanide gives the compounds [Me,SnM(Ph,P)(CO),],
[Ph,PAuIr(CO),Ph,P], and [Ph,P*Ir(CO),],Hg, (M = Ir, Rh).169
The use of insertion reactions for the preparation of metal-metal
bonds has been applied to give the complexes [C,H5Fe(CO)2],SnC1,,170
[(CO),LCo],SnX, [X = C1, Br, I ; L = CO, Ph,P, (PhO),P, B U , P ] , ~172 ~ ~and
,
[C5H,(CO)Ni],SbC1,,171when stannous halides are used. Other Group I11 or
IV halides can also participate in insertion reactions, and thus the compounds
[C,H,Fe(CO),],GeI,, [Co(CO),],InBr,THF, and XGa[Co(CO),],, THF
(X = Br, I) 172 have been prepared. The germanium compound may react
with methyl-lithium or borohydride to give the adducts X,Ge[Co(CO),],
162 D. J. Cook and R. D. W. Kemmitt, Chern. a n d Ind., 1966, 946.
163 D. J. Cardin and M. F. Lappert, Chem. Comm., 1966, 506.
164 H. R. H. Patil and W. A. G. Graham, I n o r g . Chem., 1966,5, 1401.
166 W. Jetz, P. B. Simons, J. A. J. Thompson, and W. A, G. Graham, I n o r g . C h m . ,
1966, 2217.
H. P. Weber and R. F. Bryan, C h .Comm., 1966, 443.
16' J. D. Cotton, J. Duckworth, S. A. R. &ox, P. F. Lindley, I. Paul, F. G. A. Stone,
and P. Woodward, Chem. Comm., 1966, 253.
D. J. Patmore and W. A. G. Graham, Inorg. Chem., 1966, 5, 2222.
169 J. P. Collman, F. D. Vastine, and W. R. Roper, J. Amer. Chem. Xoc., 1966, 88,
5035.
170 C. Edmondson and M. J. Newlands, Chern. and Ind., 1966, 1888.
171 D. J. Patmore and W. A. G. Graham, Inorg. Chem., 1966, 5, 1405.
F. Ronati, 8. Cenini, D. Morellj, and R . Ugo, J. Chem. Xoc. ( A ) ,1966. 1052.
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(X = Me, H).l75 The details have been given 174 for insertion of fluoro-
olefins between the tin and manganese atoms in Me,Sn-Mn(CO),, briefly
reported last year. This is in contrast with the results for the corresponding
reactions of the compound Me,GeMn(C0),.175
OrganometaUic Compounds of the Transition Metals

+Bonded Organometallic Compounds.-Reaction of dicyclopentadienyl-
zirconium &chloride 176 with triethylaluminium is comidered to give the
bridging group ZP-CH,CH2-ZrIV. The reaction 77 of diphenylacetylene
with biscyclopentadienyltitanium dicarbonyl gives the titanium heterocyclic
ring (1).
The unstable alkyl zirconium methyl complexes Zr(CH,), and Li,Zr(CH,)6

have been observed in the reaction between methyl-lithium and zirconium
tetrachloride.l78 Reduction of alkyl halides and olefins with chromous salts
is considered to involve chromium(m)-ally1 intermediates.179~l80 The
kinetics of hydrolysis and the kinetics of the reaction of mercury chloride
with six complex penta-aquopyridiomethylchromium(m) ions are re-
ported.lgl The preparation of some benzyl-chromium(m) complexes,
[CrC&(py),L] (L = benzyl, o-chlorobenzyl, p-chlorobenzyl) has been re-
ported, and the use of these as sources of benzyl anions and radicals has
been investigated.ls2 The conversion of o-aryl chromium complexes of the
type R3Cr(THP), into n-complexes by suitable solvents has been studied;
whereas conversion was possible with the ligands C,H,-C,H, and CH,c,H,,
the trimesityl complex failed to rearrange.lB3 The X-ray structure of one
of the first o-bonded arylchromium(m) complexes, CI,Cr(THF)#-tolyI, has
been published. The (3-0bond trans to the p-tolyl group is significantly
longer than the other two Cr-0 bonds (3-21 and 2.04& respectively) and
this is attributed to a trans effect of the p-tolyl group.lg4 A series of aryl-
173 N. Flitcroft, D. A. Harbourne, I. Paul, P. M. Tucker, and F. G . A. Stone, J . Chem.
SOC.( A ) ,1966, 1130.
174 D. J. Patmore and W. A. G. Graham, Inorg. Chem., 1966, 5, 1586; H. C. Clark
and J. H. Tsai, &d., p. 1407.
175 H. C. Clark, J. D. Cotton, and J. H. Tsai, Inorg. Chem., 1966, 5, 1582.
176 H. Sinn and E. Kolk, J . Organometallic Chem., 1966, 373.
177 K. Sonogashira and N. Hagihara, Bull. Chem. SOC. Japan, 1966, 39, 1178.
178 H. J. Berthold and G. Groh, Awgew. Chem., 1966, 78, 495.
17n C. E. Castro, R. 0. Stephens, and S. MojB, J . Amer. Chem. SOC.,1966, 88, 4964.
180 J. K. Kochi and P. E. Mocadlo, J . Amer. Chem. SOC., 1966, 88,4094.
181 R. 0. Coombes and M. D. Johnson, J . C h m . SOC. ( A ) ,1966, 1805.
( A ) ,1966,177; R. P. A. Sneeden,
182 R. G . Coombes and M. D. Johnson, J . C h m . SOC.
H. P. Throndsen, J . Organometallic Chem., 1966, 6, 542.
18s G. Stolze, J . Organometallic Chem., 1966, 6, 383; G. Stolze and J. Hlihle, ibid.,
p. 645.
lS4 J. J. Daly, R. P. A. Sneeden, and H. H. Zeiss, J . Amer. C h m . SOC., 1966, 88,
4287.
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E O H L A N D LEWIS : TRANSITION-METAL CARBONYLS 223
chromium(m) aryl complexes related to some of the allyl derivatives dis-
cussed in the previous Report has been obtained. The complex
Na,[Cr( C,H,),Et20],2Ef,O has been obtained in diethyl ether from phenyl-
sodium and CrCI,, (THF),. With excess of phenylsodium the hexaphenyl

complex Na,[Cr(C,H,),,xEt,O] is obtained; it is only stable in excess of
phenylsodium.185 Reaction of the pentaphenyl compound with the
chromium trichloride adduct, CrCl,,(THF), in diethyl ether yields the
complex Na,[ Cr,( C6H,),,3Et,0]. Chromium(II) phenyl derivatives may be
obtained by reduction of the corresponding chromium(m) phenyl complexes
with the production of biphenyl. The reduced paramagnetism of these
derivatives is associated with the presence of chromium-chromium inter-
action of the type observed in chromous acetate.ls6
A a-bemyl derivative of the composition C,H,( CO),MoCH,C6H5 has been
prepared from the reaction of benzyl chloride with the cyclopentadienyl-
tricarbonylmolybdenum anion. On irradiation in hexane solution this is
converted into a n-benzyl derivative C,H&H,MO(C~)~( C,H,) (see below).l8'
The reaction of chloromethyl isocyanate, with the same molybdenum anion,
yields the complex [(CO),C,H,MoCH&CO] ; with the corresponding iron
anion, [FeC,H,( CO),] -, the compound (C,H,),Fe,( CO),( CH,NCO) was
obtained.l88 The preparation of the &st aryl-rhenium complexes has been
given; the complexes formed are [Re(R),(PR,),], [ReR,(PR,),],, and
[ReNR,(PR,),] (R : Ph, CH,C,H,; PR, = Ph,P or Et,PhP).lsg The X-ray
structure of the iron carbonyl adduct with the Schiff base from p-toluidine
and benzaldehyde has been reported. In [MeC,H,NCH,C,H,]E"e,( CO),, both
o- and n-bonding between the iron and the arene ring are involved (2).
With the azobenzene adduct [Fe(CO),],PhN=NPh, a different structure is
obtained, with rupture of the nitrogen-nitrogen bond and rearrangement
to form a o-semidine skeleton.lS0
The preparation and structure of stable allyl cobaloximes RCo(D,H,)B

(R = alkyl; D = dianion of 1,2-dioximes; B = base) has been established.
The relationship of those systems to vitamin B,, derivatives is considered,
and binuclear cobaloximes containing the unit Co(CH,),Co (n = 3,4)have
lS6 F. Hein and K. Schmiedeknecht, J . Organometallic Chem., 1966, 5, 454.
ls6 F. Hein and K. Schrniedeknecht, J . Organometallic Chem., 1966, 6, 45.
la7 R. B. King and A. Fronzaglia, J. Amer. Cherra. SOC.,1966,88, 709.
R. B. King and M. B . Bisnette, Inorg. Chem., 1966, 5, 306.
J. Chatt, J. D. Garforth, and G. A. Rowe, J . Chena. Soc. ( A ) , 1966, 1834.
l g oP. E. Baikie and 0. S. Milk, Chem. C o m . , 1966, 707.
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been synthesised.lgl The preparation of an extensive series of alkyl and

aryl derivatives of cobalt(m) aetioporphyrin has been reported. The n.m.r.
signals of the protons of the alkyl derivatives fall in the range z 1 6 1 5 .
Crystalline ethyl and p-tolyl derivatives of iron(m) zetioporphyrin have

also been obtained.192 The stable organo-compounds RCo(BAE) and
RCo(BAE33,O (BAE = bisacetylacetone-ethylenediamine; R = CH,, C,H,,
C,H,) have been formed by the reaction of Grignard reagents or aryl-lithium
with the complexes [Co(BAE)(NH,),]Br or [Co(BAE)PPh,Br].lS3 The
utility of diethylbisbipyridylcobalt as a butadiene dimerisation catalyst has
been exp10red.l~~The reaction of methyl Grignard reagents with the new
complex C,H,CoI,Ph,P leads to the dimethyl derivative.lg5 Rhodium@)
methyl adducts have been obtained by oxidative addition of methyl iodide
to Rh' complexes; with the complex (Ph,P),RhCl the complex
RhIMe(Ph,P),(MeI) was 0btained.1~~ The reaction of methyl iodide (and
bromide)with the biscarbonylchloro-rhodiumdimer in the presence of sodium
cyanide yields the complex K2[MeRh(CN),(H,0)].197 The reaction of
ethylene with the hydride obtained from the action of hydrogen chloride gas
on the complex (Ph,P),RhCl in chloroform solution yields the ethyl complex
(PPh,),RhC,H,Cl, ; with acetylene a vinyl adduct (PPh,),Rh( CH=CH,)CI,
is obtained.198 The interaction of acrylonitrile and rhodium trichloride-
pyridine yields a o-bonded complex (py),RhCI,-CH( CH,)CN, the same
ligand was Qbserved when the hydride (Ph,MeAs),RhHCI, reacted with
acrylonitrile to give ( P ~ ~ ~ A S ) , R ~ C ~ , ~ C H Some
( M ~ )trimethyl-
CN.~~~
iridium phosphine derivatives Me,Ir(PR,) were obtained from the chloro-
phosphine complexes by reaction with Grignard reagents ;lg9a similar
reaction occurs with tris(dimethy1 sulphide)rhodium(m) chloride, to give
the binuclear complex (Me,S),Me,Rh,I, which was transformed into the
cyclopentadienyl complex C,H,RhMe,( SMe,) . The structures of these com-
plexes are elucidated from the 103Rh-lH coupling constants.200 The pre-
parations of the a-bonded nickel complexes R,Ni(bipy) (R = Me, Et),201s202
trans-NiXR(PMe,Ph),, and trans-NiR,(PMe,Ph), (R = o-tolyl, mesityl,
naphthyl, pentachlorophenyl, pentafluorophenyl; X halogen) ,03 have
5
been given. It was shown that the ligand tris-2-(2-biphenylyl) phosphite
lgl G. N. Schrauzer and R. J. Windgassen, J. Amer. Chem. SOC.,1966, 88, 3738;

G. N. Schrauzer and R. J. Windgassen, Chena. Ber.,1966, 99, 602.
l e aD. A. Clarke, R. Grigg, and A. W. Johnson, Chem. Comrn., 1966, 208.
lQ3 G. Costa, G. Mestroni, G. Tauzher, and L. Stefani, J. Organometallic Chem., 1966,
6, 181.
lQ4 T. Saito, Y.Uchida, A. Misono, A. Yamarnoto, K. Morifuji, and S. Ikeda, J.
Organometallic Chem., 1966, 6, 572.
l Q 5 R. B. King, Inorg. Chem., 1966, 5, 82.
D. N. Lawson, J. A. Osborn, G. Wilkinson, J. Chem. SOC.( A ) , 1966, 1733; M. C.
Baird, D. N. Lawson, J. T. Mague, J. A. Osborn, and G . Wilkinson, Chem. Comm.,
1966, 129.
1 Q 7 JP.. Maher, Chem. Comm., 1966, 785.
lQ* K. C. Dewhurst, Inorg. Chem., 1966, 5, 319.
lQ9 J. Chatt and B. L. Shaw, J. Chem. SOC.( A ) ,1966, 1836.
2 o o H. P. Fritz and K. E. Schwarzhans, J. Organometallk Chem.,,.1966, 5, 283.
201 T. Saita, Y.Ushida, A. Misono, A. Yamamoto, K. Morifuji, and S. I. Keda,
J . Amer. Chem. Xoc., 1966, 88, 5198.
2 0 2 G. E. Wilke and E. Herrman, Angew. Chem., 1966, 78, 591.
203 J. R. Moss and B. L. Shaw, J. Chem. SOC.( A ) ,1966 1793.
View Article Online
stabilisesnickel-carbona-bonds in the complex [(C6H,-C,H4O),P],Ni( CH,),. 202
A variety of allyl, aryl, and alkynyl nickel cyclopentadienyl compounds
of the type C,H,Ni(L)(R) (L = phosphine, arsine, stibine) has also been
0btained.20~ Bistritylnickel was obtained by the interaction of bis-(cyclo-

octa-1,3-diene)nickel(O)with hexaphenylethane, or nickel acetylacetone with
hexaphenylethane in the presence of diethylahminium ethoxide. The
pure solid compound is not air-sensitive but decomposes in argon at 120'0
and reacts with triphenylphosphine to give the tetrakistriphenylphosphine-
nickel(0) ~omplex,~O~
(Ph,C),Ni + 4PPh, +Ni(PPh,), + Ph,C--CPh,.
A novel method for the preparation of ally1 derivatives of pIatinum(lr)
has been observed ; octene reacts with lithium tetrachloroplatinate(n) in
the presence of formic acid in dimethylformamide to give [octylPt(CO)ClJ,
which with acetylacetone and triphenylphosphine yields [octylPt(CO)(acac)]
and the acyl adduct [octyl-C0.Pt(Ph3P),C1].206 The nature of a series of
platinum-carbon bonded @-diketonecompounds has been investigated, and
the utilisation of the unco-orhated carbonyl oxygens of these complexes
as potential donor groups el~cidated.~O7The X-ray structures of some cyclo-
propane complexes of platinum have been determined. The complex
C3H,Ptpy2C12 has been found to have a four-membered carbon-platinum
Et
H'
--c I
lb
ring system, whilst reaction of this complex with carbon tetrachloride or
chloroform gives a compound having the structure shown in (3). The
bonding between the carbon group and the platinum is considered to be
an ylide rather than a carbene structure.208 Bromination of the a-allyl-
phenyldimethylarsine (L) complex of platinum, PtBr,( L)2, has been shown
to lead to the formation of a platinum-carbon bond with concomitant
rearrangement of one of the allyl arsine derivatives to give an isopropy
grouping. An X-ray structure analysis of the ethoxy-derivative has been
carried out.209 The n.m.r. spectra of a large number of trimethylplatinum(rv)
H. Yamazaki, T. Nishido, Y .Hatsumoto, S.Sumida, and M.Hagihara, J . Organo-
metallic Chem., 1966, 6, 86.
,05 (3. Wilke and H. Schott, Angew. Chem., 1966, 78, 592.
2 0 6 D. Wright, Che'Ln. Comm., 1966, 197.
$07 D. Gibson, J. Lewis, C. Oldham, J. C h m . SOC.( A ) , 1966, 1453; J. Lewis and
C. Oldham, ibid., p. 1456.
2 0 8 W. A. Bailey, R. D. Gillard, M. Keeton, R. Mason, D. R. Russel, Chem. Comm.,
1966, 396.
* O 0 M. A. Bennett, G. J. Erskine, J. Lewis, R. Mason,R. S.Nyholm, G. B. Robertson,
and A. D. C. Towl, Chem. Cmm., 1966, 395.
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226 INORffANIC CHEMISTRY
derivatives have been obtained,210 and the structure of the hydroxy-

compound, [Me,PtOH],, determined from n.m.r. and infrared data.211 The
conditions for the preparation of almost pure phenylcopper were reported.212
A carbon-bondedp-diketone adduct of gold@)has been prepared by reaction

of triphenylphosphine gold halides with thallous a~etylacetone.21~
The X-ray structure of ethyl zinc iodide indicates that it is a co-ordinated
polymer with iodide bridges.214 The molecularity of a series of alkylzinc
derivatives in benzene has been determined.215 The X-ray structure of
methyl zinc methoxide shows it to have a tetrameric structure with the zinc
atom a t the corners of a tetrahedron.216
The search for metal carbene complexes has continued during the past
year. The X-ray structure of the methylmethoxycarbene-phosphine com-
plex, Me(MeO)C.Cr(CO),(PPh,),has been carried The presence of a
metal carbene intermediate has been postulated in the reaction of tetra-
fluoroboric acid with the compound C,H,Fe( CO)2CH,0Me as the complex
[C,H,Fe(CO),CH,] +BF,- ; norcarane is formed if the reaction is performed
in the presence of cyclohexene, and cis-but-2-eneis transformed into cis-l,2-
dimethylpropane.21*Di-p-dichloro-bis-n-allyldipalladium (4) is considered to
react with diazoacetate to give a carbene intermediate, as alkenes are con-
verted into cyclopropane carboxylic esters.219
,,CH
(allyl)Pd,
CI
*C02Et
RzC=CRz +
5
I >C.H+CO,Et
L
J R?
Dfazomethane reacts with the complex (Ph,P),IrCQCl to give a methylene
insertion reaction, with the formation of (Ph,P),IrCO(CH,Cl). The reactivity
of the product is explained in terms of the conversion into a methylene
carbene intermediate from the chloromethyl group.220
A series of vinyl-metal complexes has been obtained. The reaction of
diphenylketen with iron pentacarbonyl gives a compound whose X-ray
structure establishes the complex as diphenylvinylideneoctncarbonyldi-
iron.221 A new cyclopentadienyl oxy-a-vinyliron group has been identified
alo K. Kite, J. A. S. Smith, and E. J. Wilkins, J . Chew,. SOC.( A ) ,1966, 1744.
G . L. Morgan, R. D. Rennick, and C. C. Soong, Inorg. C h m . , 1966, 5, 372.
21a G. Costa, A. Camus, L. Gatti, and N. Marsich, J. Organonzetallic Chem., 1966,
5, 568.
ala D. Gibson, B. F. 0.Johnson,J. Lewis, and C. Oldham, Chem. and Ind., 1966,342.
214 P. T. Rloseley and H. M. M. Sheerer, Chem. Comm., 1966, 876.
$16 J. Boersma and J. G . Nottes, Tetrahedron Letters, 1966, 1521; G . E. Coates and
D. Ridley, J. Chenz. Soc. ( A ) , 1966, 1064.
216 H. M. M. Shearer and C. B. Spencer, C h m . Comm., 1966, 194.
*17 0. S. Mills and A. D. Redhouse, Chem. Comm., 1966, 814.
P. W. Jolly and R. Pettit, J. Amer. Chem. Soc., 1966, 88, 5044.
R. I(.Armstrong, J. Org. Chem., 1966, 31, 618.
2 2 0 F. D. Mango and I. Dvoretzky, J. Amer. C h m . SOC., 1966, 88, 1654.
z 2 1 0. S. Mills and A. D. Redhouse, Chem. Comm., 1966, 444.
View Article Online
KOHL AND LEWIS : TRANSITION-METAL CARBONYLS 227
from the X-ray structure of one of the reaction products from the interaction
of iron pentacarbonyl with methylphenylpropiolate 222 (5).
COzMe
co
c=c'
Ph' 'C02Me
The reaction of acetylene with the hydride (Ph3P),RhHC1, yields the
vinyl complex (Ph,P),RhCl,( CHCH,).lS6 l-Chloro-2,2-diphenylvinylsilver
has been obtained from the metathesis of the lithium compound and silver
chloride. 223
Fluorine-containing a-Carbon Complexes.-The 19E' n.m.r. spectra of m-
and p-fluorophenylplatium(n) compounds have been utilised t o indicate
the relative n and 0 properties of other ligands in the molecule.224 The
preparation of the compound (C,H,),Zr(C,E",), has been given; the compound
is chemically less robust than the titanium derivative.225 The comparison
of the metal-carbon bond lengths obtained by X-ray structure analysis o
the complexes C,H,Mo(CO),X (X = C3F, and C,H5) indicates the presence
of n-bonding in the metal-carbon bond 226 for the fluorine compound. The
reaction of pentafluorobenzenethiol with the pentacarbonyl hydrides cf
manganese and rhenium yields the pentafluorophenylpentacarbonyl com-
plexes C,F,M(CO), (M = a, Re) ;87 pentafluoropyridine and pentafluoro-
benzonitrile react with manganese and rhenium pentacarbonyl anions t o
give the 3-substituted tetrafluoropyridine and tetrafluorobenzonitrile penta-
carbonyl adducts, respectively. 227 The reaction of lithium pentafluorophenyl
with the cation [C,H,Fe(CO),]+ gives a mixture of the pentafluorobenzoyl
complex C,H,Fe( C0),COC6F, and the 0-bonded pentafluorophenyl com-
pound C,H,Fe (CO),-C,F5 ; in contrast, the corresponding triphenylphosphine
cation, [C,H,Fe( CO),PPh,] f, reacts to give addition of a pentafluorophenyl
group to the cyclopentadienyl ring with formation of a diene complex,
(C,M,C,F,)Fe(CO)2(YPh3).228 The higher stability of metal-carbon o-bonds
in fluoro-complexes is emphasised in the reaction of hexa>fluorobut-Zyne
with the rhenium peiitacarbonyl amnion,yielding the first allene in which a
o-bond to a tramition metal occurs, [(F2C=C=C) (CF,)*Re(CO),];a substituted
fluorocyclobuta,iie adduct is also obtained. 229 a-Bonded rhenium peiita-
carbony1 and cyclopentadienyliron dicarbonyl adducts of perfluorobuta-1,3-
diene have besn reported.229 The interaction of fluorinated olefins and
2 t 2 L. F. Dahl, R. J. Doedens, W. Hubel, and J. Nielsen, J. A m r . Chenz. Soc.,
1966, 88, 446.
223 G . Kobrich, H. Frohlich, and W. Drischel, J . OrgunometuZZic Chem., 1966, 6, 194.
2 2 4 E. W. Parshall, J. Amer. Chem. SOC.,1966, 88, 704.
2 a 5 M. A. Chaudhari and F. G. A. Stone, J . Chem. SOC. ( A ) ,1966, 838.
2 2 6 M. R. Churchill and J. P. Fennessey, Chsm. Comm., 1966, 695.
2 2 7 B. C. Booth, R. N. Haszeldine, and M. €3. Taylor, J. Urgunometallic Chem., 1966,
6, 570.
P. M. Treichel and R. L. Shubkin, J . Orgunometallic Chem., 1966, 5, 488.
2 2 8 M. Green, W. Mayne, and F. G. A. Stone, Chem. Comm., 1966, 755.
View Article Online
substituted fluorinated benzene compounds with manganese and rhenium

pentacarbonyl anion and cyclopentadienyl iron dicarbonyl anion leads to
the formation of complexes with metal-carbon ~ - b o n d s . ~ ~Heptafluoro-
O
propyl iodide is found to react with the compound C,H,Co(CO)PPh, to yield

C,H,COI(C~F,)PP~,.~~~A new tetranuclear nickel cluster, [(CF3),C,],Ni,(C0),,
has been obtained from the interaction of hexafluorobut-2yne and nickel
carbonyl ; the compound is formulated as involving hexafluorobut-2-ene
bridges.231 Perftuorovinyl complexes of platinum have been prepared by
reaction of fluoro-olefins 232 and fluoroacetylenes152 with platinum phos-
phine hydride complexes, whilst addition of fluoro-olefins to tetrakistri-
phenylphosphineplatinum(0) yields the cyclic o-bonded complexes (6).
(6)
Reaction with perfluoroacetone yields a novel three-membered ring complex
in which the platinum bonds to both the oxygen and the carbon of the per-
fluoroacetone molecule, (Ph3P),Pt(CF3)2C0.233Addition of fluoro-acetylene
complexes to tetrakistriphenylphosphine complexes of palladium 234 and
platinum 152 yield the bistriphenylphosphine cyclic a-bonded olefin metal
complexes (Ph,P),M(C,RR) (M = Pd, R = R’ = CP3; M = Pt, R’ = CF,,
R = H). Complexes of bisperfluoroallyl mercuric complexes with a variety
of oxygen and nitrogen ligands have been described.235
Carbonylation and Related Reactions.-The stereochemistry of carbonyl
insertion reactions of methylmanganese pentaFarbony1 using phosphines as
the attacking ligands has been studied; a stereospecific reaction to give the
cis-acyl adduct has been observed with the phosphine P(OCH,),-CCH3. 236
The presence of rotational isomers in the acylpentacarbonyl manganese
system, CXH,COMn(CO),, CHX,COMn(CO), (X = F, Cl) has been detected
by infrared measurements over a range of temperature.237 The variation in
the formation of acyl compounds with metal complex has been extended
by a study involving some novel ligand molecules. 2-Chloroethyldimethyl-
amine reacts with the iron anion [Fe(CO),(C,H,)]- to give the acyl complex
[Me,NCH,CH,COFeCO(C,H,)I and the salt
[C5H5Fe(CO),*NMe2CH2CH2Fe( CO),C,H,]CZ ;N-l-chloroethylpiperidinereacts
to give C,H1oNCH,CH,Fe( CO),C,H,, and analogous complexes are obtained
with 2-chloromethylpyridine with both the anions [Fe(CO),(C,H,)]- and
( A ) ,1966,1837; M. I. Bruce, P. W.
a 3 0 M. I. Bruce and F. G. A. Stone, J . Chern. SOC.
Jolly, and F. 0. A. Stone, ibid., p. 1602.
231 R. B. King, M. I. Bruce, J. R. Philips, and F. G. A. Stone, Inorg. Chern., 1966,
5, 684.
H. C. Clark and W. S. Tsang, Chem. Comm., 1966, 123.
z33 M. Green, R. B. L. Osborn, A. J. Rest, and F. G. A. Stone, Chem. Comm., 1966,
602.
234 E. 0. Greaves and P. M. Maitlis, J . Organometallic Chem., 1966, 6, 104.
zs6 H. B. Powell and J. J. Lagowski, J . Chern. SOC.( A ) ,1966, 1282.
z36 M. Green and D. C. Wood, J . Amer. Chem. SOC.,1966,88, 4106.
3 3 7 F. Cdderazzo, K. Noack, and U. Schaerer, J. Organometallic Chem., 1966,6, 265.
View Article Online
E O H L A N D L E W I S : T R A N S I T I O N - M E T A LC A R B O N Y L S 229
[W(CO),C,H,]-. With the molybdenum anion [n-C,H,Mo(CO),]-, however,
2-chloropyridine yields an acyl complex, [NC,H,CH,COMo( CO),C5H5].
The manganese pentacarbonyl anion gives a cyclic acyl product with
2-chloroethyldimethylamine,[NMe,CH,CH,COMn( CO),], and with 2-chloro-

methylpyridine [NC,H,CH,COMn( CO),].238
Acyl derivatives of the type trans-[MX(COR)(PEt,),] (M = Pd, P t ;
X = Cl,Br, I, R = Me, Et, or Ph) have been obtained by the reaction of
carbon monoxide with the appropriate alkyl or aryl c0mplex.23~
Insertion reactions analogous to carbonylation have been found to occur
with sulphur dioxide, to yield Mn(CO)&302Rcomplexes (R = Me; CH,Ph)
by reaction of the alkyl pentacarbonyl manganese with liquid sulphur
dioxide.240 A large range of cyclopentadienyl iron sulphinatodicarbonyl
complexes is obtained by a similar process, and alternative methods of pre-
paring these compounds have been illustrated. 241
Decarbonylations of a variety of organic acyl and aryl compounds with
the complex (Ph,P),RhCl have been investigated.242
Olefin-Metal Complexes.-The mechanism of the isomerisation of olefins
by transition-metal ions has been discussed in terms of the alkyl and ally1
the0ries,24~and the mechanism of hydrogen migration in cycloheptatriene-
molybdenum tricarbonyl complexes has been
Mono-o1efins.-The kinetics and mechanism of the hydrolysis of the
palladium-ethylene system to acetaldelyde have been investigated.245 A
molecular orbital treatment of the ultraviolet polarised crystal spectrum of
Zeise’s salt, K[Pt(C,H,)Cl,]H,O, has been reported.246 The proton n.m.r.
spectra of Zeise’s salt and related molecules have been used to determine the
orientation of the olefin to the plane of the platinum-chlorine system.247
The far-infrared spectra of a series of ethylene-platinum complexes have
been observed,2**and a normal co-ordinate analysis of the infrared spectra
of Zeise’s salt was carried 0ut.2~9
A number of compounds have been reported in which, in addition to
co-ordination of the olefin, bonding of the ligand occurs a t other centres.
1 1
Iq the complex Me,AsC=C(AsMe,)CF,CF,[Fe( CO),], one of the iron atoms is
octahedrally co-ordinated to three CO groups and the two arsenic atoms with
a metal-metal bond in the sixth position; the remaining iron has trigonal-
bipyramidal stereochemistry with three carbonyl groups, a metal-metal
238 R. B. King and M. B. Bisnette, Inorg. Chem., 1966, 5, 293.

23s G. Booth and J. Chatt, J. C h .SOC.( A ) , 1966, 634.
e 4 0 I?. A. Hartman and A. Wojcicki, J. A m r . Cham.Soc., 1966, 88, 844.
241 J. P. Bibler and A. Wojcicki J. Amer. Chem. SOC.,1966, 88, 4862.
J. Tsuji and K. Ohno, J . Amer. Chem. SOC.,1966,88,3452; J. Blum, Tetrahedron
Letters, 1966, 1605; J. Tsuji and K. Ohno, ibid., p. 4713.
ars R. Cramer, J. A m . Chem. SOC.,1966, 88, 2272; R. Cramer and R. V. Lindsey,
ibid., p. 3534.
2 4 4 W. R. Roth and W. Grimme, Tetrahedron Letters, 1966, 2347.
a p 5 R.Jira, J. Sedlmeier, and J. Smidt, Annakn, 1966, 693, 99.
J. W . Moore, Acta Chem. S c a d . , 1966, 20, 1154.
a 4 7 H. P. Fritz, K. E. Schwarzhans, and D. Sellman, J. OrganometaUic Chem., 1966,
8, 551.
2 4 a H. P. Fritz and D. Sellmann, J. Organometdic Chem., 1966, 6 , 558.
2 4 9 M. J. Grogan and K. Nekamoto, J. Amer. Chem. SOC., 1966, 88, 5454.
View Article Online
bond, and co-ordination to the olefin group of the cyclobutene ring.250

The ligand 2-allylphenyldiphenylphosphine(AP), CH,=CH*CH,*C6H4PPh2,
acts as a chelate with an olefin and phosphorus group bonding to give the
compounds (AP)M(CO), (M = Cr, Mo, W),251whilst in the complex trans-

2,2'-di-(di-o-tolylphosphino)stilbenerhodium chloride, the organic group acts
as a terdentate ligand, bonding by two phosphorus atoms and the o l e h
group.252 A new type of zerovalent metal complex tris(methy1vinyl ketone)-
tungsten has been reported; co-ordination of both the olefm and the 6 0
group to give a bidentate chelate are postulated.66
The photochemical preparation of some new iron tetracarbonyl complexes
of vinyl chloride, styrene, propene, and ethyl vinyl ether is reported. The
infrared data imply that the organic groups are co-ordinated through their
olefinic double bond.252 The X-ray structure of the fumaric acid-iron
tetracarbonyl complex confirms that co-ordination of the acid to the metal
occurs through the double bond. 253 A series of gold chloride olefin complexes
with a large range of cyclic mono- and di-olefins has been reported.254 The
X-ray structures of the following silver(1) olefin adducts have been carried
out : the norbornadiene adduct C,H,,2AgN0,,255 the bulvalene complex
CloHlo,3AgBF4,256and the complex C6H,-Ag*AlC1,.257The structure of the
copper complex C6H,CdC1, is analogous to that of the benzene silver
complex.25,
Polyene Systems.-The study of the proton n.m.r. spectra over a tempera-
ture range for a series of cyclo-octatetraene metal carbonyls, C,H,M(CO),
(M = Cr, Mo, Pe), together with 1,3,5,7-tetramethylcyclo-octafefraene-
molybdenum tricarbonyl and an extensive range of substituted cyclo-octa-
tetraeneiron tricarbonyl adducts, indicates the presence of valence tautomer-
isation in these systems. The bonding of the complexes has been interpreted
in favour of both 1,3-diene and 1,5-diene co-ordination of the ring system
to the metals.259 For the tungsten analogue, c,H,w(Co),,the n.m.r. spectra
a t room temperature show the anticipated four sets of hydrogen signals.66
From the n.m.r. spectrum, valency tautomerism has also been suggested to
be present in cyclo-octatetraenecobalt cyclopentadienyl.260 In both the
cyclobutadiene and butadiene iron tricarbonyls, carbon-13 and proton n.m.r.
spectra have been interpreted as indicating that the carbon atoms involve
s60 F. W. B. Einstein, W. R. Cullen, and J. Trotter, J . Amer. Chern. Soc., 1966, 88,
6670.
'ti1 I;. V. Interraate, M. A. Bennett, and R. S. Nyholm, Inorg. Chem., 1966, 5, 2212.
M. A. Bennett, R. Bramley, and P. A. Longstaff, C h m . Comm., 1966,806; E . K.
von Gustorf, M. C. Henry, and C. Di Pietro, 2.Nalurforsch., 1966, 21b, 42.
P. Corrandi, C. Pedone, and A. Sirigu, Chem. C m n . , 1966, 341.
2 5 4 R. Huttel, H. Reinheimer, and H. Dietl, C h m . Ber., 1966, 99, 462; R. Huttel
and H. Reinheher, ibid., p. 2778.
2 5 6 N. C. Baenziger, H. L. Haight, R. Alexander, and J. R. Doyle, Inorg. Chem.,
1966, 5, 1399.
2 6 6 M. Gary Newton and I. C. Paul, J . Amer. Chem. SOC., 1966, 88, 3161.
2 5 7 R. W. Turner and E. L. Amma, J . A w . Chem. SOC., 1966,88, 3243.
2 s 8 R. W. Turner and E. L. Amma, J . A w . Chem. SOC.. 1!366,88, 1877.
2 5 9 C. E. Keller, B. A. Shoulders and R. Pettit, J . Amer. Chem. Soc., 1966, 88, 4760;
C. G . Kreiter, A. Maasbol, E. A. L. Anet, H. 0. Kaesz, and S. Winstein, ibid., p. 3444;
F. A. Cotton, J. W. Faller, and A. MUSCO,ibid., p. 4506; F. A. Cotton, A. Davison, and
.W. Faller, ibid., p. 4507.
2 6 0 S. Otsuka and A. Nakamura, Inorg. Chem., 1966, 5, 2059.
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K O H L A N D LEWIS: T R A N S I T I O N - M E T A L CARBONYLS 231
essentially sp2-hybridisa.tion,and are consistent with bonding of the dienes
to the metal in a similar manner to the ferrocene system.261
It has been found possible to add 1 mol. of carbon monoxide to the
complexes C,H,Mo(CO), and (cyclo-octa-l,3,5-triene)Mo(CO), to yield

the tetracarbonyl complexes. The n.m.r. proton spectra indicate that
in the resultant complex the ligands are co-ordinated as 1,5-cyclo-octa-
tetraene and 1,5-cyclo-octatrieneadducts.26s
The reaction of triphenylphosphine with a series of dieneiron tricarbonyl
complexes to yield some triphenylphosphineiron dicarbonyl diene com-
plexes 263 has been studied. Vitamin A aldehyde reacts with iron penta-
carbonyl to give a diene iron tricarbonyl complex. The X-ray structure of
this compound has been determined.264 A number of /?-ionone iron tri-
carbonyl compounds have been prepared, and their properties reported.265
Butadiene reacts with ruthenium trichloride in 2-methoxyethanol to
give dichloro(deca-2,6,10-triene-1,12-diyl)ruthenium(1v).~~~ The complexes
[Ru(CO)CI,(diene)], (diene = cyclo-octa-1,5-diene and norbornadiene) have
been ~repared.~67Reaction of titanium tetrakisbutoxide with cyclo-octa-
tetraene in the presence of triethylaluminium produces bis(cyclo-octa-
tetraene)titanium and the dimer Ti,(COT), 268 (7) ; the crystal structure of
the dimer has been determined; a series of new n-complexes of iron(0) and
ruthenium(0) with seven- and eight-membered cyclic olefins have been pre-
pared, and the n.m.r. spectra of these complexes assigned.,'*
The use of the intermediates [(olefin),RhCI], (olefin = cyclo-octene,
cycloheptene, and norbornene) for the preparation of a series of diolefh
compounds, [(dioleh),RhCl], has been exploited ; 271 a similar series of
reactions has been established for iridium.,' The rhodium carbonyl chloride
h e r , [Rh(CO),Cl],, reacts with cyclohexa-1,3-diene and 2,3-dimethyl-
butadiene to give the adduct [Rh(CO),Cl],diene. It is suggested that the
r s l H . G. P m t o n and J. C. Davis, J . Amer. Chem. SOC.,1966, 88, 1585; H. L.
Retcofsky, E. W. Franke1;and H. S. Gutowsky, ibid., p. 2711.
a 6 2 S. Winstein, J . Amer. Chem. SOC., 1966, 88, 1319.
a 6 3 F. M. Chaudhari and P. L. Pauson, J . O r g a m t a l l i c Chem., 1966,5, 73.
8 6 4 A. J. Birch, H. Fitton, R. Mason, G. B.Robertson, and J. E. Stangroom, Chem.
Cornm., 1966, 613.
8 8 6 M. Cais and N. Maoz, J . Organometallic Chem., 1966, 5, 370.
2 8 s J. K. Nicholson and B. L. Shaw, J. Chem. SOC. ( A ) ,1966, 807.
2 6 7 S. D. Robinson and C . Wilkinson, J . Chem. SOC.( A ) ,1966, 300.
2 6 8 H. Breil and G. Wilke, Angew. Chem., 1966, 78, 942.
H. Dietrich and H. Dierks, Angew. Chem., 1966, 78, 943.
* 7 0 J. Miiller and E. 0. Fischer, J . Organometallic Chem., 1966, 5, 275.
2 7 1 L. Porri and A. Lionetti, J . Organometallic Chem., 1966, 6, 422; G. Winkhaus
and H. Singer, Chem. Ber., 1966, 99, 3602.
2 7 2 G. Winkhaus and H. Singer,Chem. Bm., 1966, 99, 3610.
View Article Online
diene acts as an additional bridging ligand across the rhodium atoms of

the carbonyl chloride dimer.,V3 The structure of cyclo-octenylnickel(n)
acetylacetone has been determh~ed,~v~ and also that of the related platinum
complex methoxydicyclopentadienechloroplatinum dimer.275 In both com-

plexes the ligand co-ordinates through both a n-bonded metal-oleh
and a o-metal-carbon bond. The reactivity of diene-palladium and
-platinum complexes towards nucleophilic attack, with the formation of
compounds typified by the last two structures, has been studied with
acetylacetonate ani0ns~7~ and methoxide ions.277,,7* The n.m.r. spectra
of a series of methoxy-derivatives has been used to determine the stereo-
chemistry of these products. 2 7 8 The carbonylation of cyclo-octa-1,5-diene
to ethyl cyclo-octene-4-carbonylatehas been accomplished using the palla-
dium-cyclo-octa-l,5-dienechloride complex.279 Buta-1,3-diene and cyclo-
octa-l,3-dienepalladium dichloride complexes have been obtained by
ligand exchange with bisbenzonitrilepalladium dichloride or the corres-
ponding pentene complex. The diene complexes are dimers, [(diene)PdCl],,
and are considered to bond through only one olefin group. The butadiene
compound isomerises a t room temperature to a mallyl compound.280
The use of cyclobutadieneiron tricarbonyl as an intermediate in organic
chemistry for the production of cyclobutadiene has been illustrated.281 The
reaction of chloromethylcyclobutadieneiron tricarbonyl with antimony
pentachloride abstracts the chloride to give cyclobutadienemethyleneiron
tricarbonyl cations.282 Tetraphenylbutatriene reacts with iron ennea-
carbonyl to give two complexes corresponding to the addition of Fe(CO),
and Fe,(CO), units to the ligand; 2B3 the structure of the Fe(CO),L adduct
shows that the iron is co-ordinated to the central carbon double bond 284
(8).
A&l Complexes.-The isomerisation of labelled olefins by iron and cobalt

carbonyls has been interpreted in favour of an ally1 intermediate.285 The
G. Winkhaus and H. Singer, C h . Ber., 1966, 99, 3593.
274 0. S. Mills and E. F. Paulus, Chem. Comm., 1966, 738.
a15 W. A. Whitta, H. M. Powell, and L. M. Venanzi, Chem. Comm., 1966, 310.
2 7 6 B. F. G. Johnson, J. Lewis, and M. S. Subramaniam, C h m . Comm., 1966, 117.
2 7 7 R. G. Schultz, J . Organmetallic Chem., 1966, 6, 435.
2 7 8 J. K. Stille and R. A. Morgan, J . Amer. Chem. SOC., 1966, 88, 6135.
2 7 8 J. Tsuji, S. Hosaka, J. Kiji, and T. Susuki, Bull. Chem. SOC.Japan, 1966,39,141.
2 8 0 M. Donati and F. Conti, Tetrahedron Letters, in the press.
281 J. C. Barborak, L. Watts, and R. Pettit, J. Amer. Chem. SOC., 1966, 88, 1328.
J. D. Fitzpatrick, L. Watts, and R. Pettit, Tetrahedron Letters, 1966, 1299.
283 K. K. Joshi, J . Chem. SOC. ( A ) ,1966, 598, 594.
a s 4 D. Bright and 0. S . Mills, C M . Comm.,1966, 211.
4 8 5 B. Fell, P. Krings, and F. Asinger, C h m . Bw., 1966, 99, 3688.
View Article Online
bonding of n-ally1 complexes to transition metals has been discussed with
particular reference to the stereochemistry of n-allylpalladium chloride and
acetate.286 The detailed structure of acetylacetonate cyclo-octa-2,4-dienyl-
palladium is reported; 287 a co-ordinated n-aUyl and free olefin group within
the same organic ring has been established from the X-ray structural analysis
of the binuclear azulene complex Cl,H8Pe2(C0),.288 One of the products
of the reaction of cyclo-octatetraene (COT) with iron enneacarbonyl,
(COT)Fe,(CO),, has been shown to involve two symmetrically placed ally1
groups, one each bonding to an iron atom with the two remaining carbons
of the ring bonding through two three-centre bonds t o the two irons and a
bridging carbonyl group. A rapid valence tautomerism with rotation of the
iron groups around the ring is postulated 289 in order to explain the n.m.r.
rtpectra. The structure of perfluorocyclopentadienedicobalt heptacarbonyl
has shown the presence of a Co(CO), fragment a-bonded to the cyclo-
pentadiene ring and a Co(CO), group bonded via a n-ally1 system to the
ring.
The variation in the proton n.m.r. spectra over a temperature range of a
number of metal-ally1 compounds have been studied and have been inter-
preted on the basis of the presence of n-a-ally1 equilibria and rotation of the
CH, groups of the n-ally1 system; various allyl complexes of zirconium,291
rhodium,292and palladium 203 have been studied, and the n.m.r. spectra
utilised to determine the kinetics of the reaction of the complex (C4H,PdC1),
with The a-n-character of the allyl bond in the complex chloro-
(triphenylphosphine)(methylallyl)palladium(n), discussed in last year’s
Report, has been substantiated by the X-ray structure of the compound.295
However, the importance of viewing this as a n-ally1derivative rather than
a mixed n-olefin and a-carbon bonded species has been e m p h a s i ~ e d294 .~~~~
A novel n-ally1 system was identified in (n-benzy1)molybdenumcyclopenta-
dienyl tricarbonyl in which two of the carbons of the benzene ring and the
methylene carbon comprise the co-ordinated n-ally1 group. In order to
interpret the n.m.r. proton spectra of this compound it is postulated that
either the mbenzyl group may rotate about the two-fold axis of the benzyl
ring or that an equilibrium between n- and a-structures occurs.192
A new synthesis of allylbis(cyclopentadienyl)titanium(m) derivatives
has been reported. 296 The chemistry of a a-allylmolybdenum(n) complex
has been extended. One obtains a series of mononuclear allyl derivatives
286 S. F. A. Kettle and R. Mason, J . Organometallic Chem., 1966, 5, 573.
M. R. Churchill, Inorg. Chem., 1966, 5 , 1608.
2 8 8 M. R. Churchill, Chem. Comm., 1966, 450.
2 8 8 E. B. Fleischer, A. L. Stone, R. B. K. Dewar, J. D. Wright, C. E. Keller, and
R. Pettit, J . Amer. Chem. Soc., 1966, 88, 3158.
P. B. Hitchcock and R. Mason, Chem. Comm., 1966, 503.
291 J. K. Becconsdl and S. O’Brien, Chem. Comm., 1966, 302.
2 g 2 H. C. Volger and K. Vrieze, J . OrganometaZZic Chmn.,1966, 297; J. K. Becconsall
and S. O’Brien, Chem.Comm., 1966, 720.
293 G. L. Statton and K. C. Ramey, J . Arner. Chem. Soc., 1966, 88, 1327; K. C.
R a m y and G. L. Statton, ibid., p. 4387; K. Vrieze, C. Maclean, P. Cossee, and C. W.
Hilbers, Rec. Trav. chim., 1966, 85, 1077.
2 Q 4 K. Vrieze, P. Cossee, C. MacLean, and C. W. Hilbers, J . Organometallic Chena.,
1966, 6, 672.
2 Q 5 R. Mason and D. R. Russel, Chem. C m m . , 1966, 26.
2 * 6 If. A. Martin and L. Jellinek, J . Organometallic C h . ,1966, 6, 293.
View Article Online
by splitting the bridge of the salts of tri-~-chlorobis-(2-methyl-n-allyl-

dicarbonylmolybdenum) anion.297 The preparation of three acetyl- or
benzoyl-allylmanganese tetracarbonyl derivatives by interaction of methyl-
or phenyl-manganese pentacarbonyl with butadiene has been de~cribed,~Qa

and the mechanism of this reaction in~estigated.2~~ The reaction of allene
with tri-iron dodecacarbonyl and cobalt octacarbonyl has been reported. A
rapid valence tautomerism between a 2,2’-bi-n-allylenehexacarbonyl di-iron
structure and a butadiene structure is deduced from the proton n.m.r.
spectra.300 Trimethylenemethane has been stabilised as a ligand with an
iron tricarbonyl fragment by reaction of iron enneacarbonylwith 1,l-dichloro-
methylethylene, CK2=C(CH2C1),to give [(CH,),C]Fe(CO),. 301
A series of 0-and n-ally1 complexes has been isolated from the reaction
of triphenylphosphinerhodium chloride with allyl chloride in solution.302
Tris-n-allylrhodiumhas been prepared by reaction of the (bis-n-allylrhodium
chloride) h e r , [(C,H?),RhCl],, with allylmagnesium chloride. The n.m.r.
spectra indicate that each n-ally1 group is symmetrically bonded but that
they are not stereochemically e q ~ i v a l e n t302. ~ ~The
~ ~ preparation of allyl-
palladium chloride from chloropalladite and allyl chloride in the presence of
carbon monoxide is considered to occur through an oxidative hydrolysis.
This concept has been developed to prepare a number of rhodium allyl
comple~es.~0~ A series of n-ally1 and alkyl nickel phosphine compounds has
been reported ;304 the preparation of 1,4,7-trimethylenecyclononanefrom
1,I-bischloromethylethylene,(ClCH,),CCH,, and nickel carbonyl is con-
sidered to occur through a n-ally1 complex.3o5 With iron carbonyl a stable
allyl intermediate is obtained (see above).
The preparation of allylpalladium(n) anions, [(n-allyl)PdX,]- (X = halo-
geIi), is described; they are obtained by reaction of excess of halide and the
corresponding n-ally1halogen dimem306 The reaction of allene with chloro-
palladate (11) yields (p- 3- chloroprop - 1-en-2-y1)allyl and 2- chloroprop-2-enyl
palladium complexes.307
Csclopentadiene Complexes.-T he analogy between metal-carb orane
derivatives and cyclopentadienyl compounds is emphasised by the X-ray
structure determination 308 of the anion, [(B,C,H,,)Re(CO),], which has the
structure previously proposed.309 The complexes of carboranes with palla-
dium(n) have been established with the preparation of the tetraphenylcyclo-
2Q7 H. D. Murdoch and R. Henzi, J. Organometallic Chem., 1966, 5, 552.

298 W. D. Bannister, M. Green, and R. N. Haszeldine, J . Chem. SOC.( A ) ,1966, 194.
2 9 s M. Green and R. I. Hancock, Chem. Comm., 1966, 572.
3 0 0 A. Nakamura, Bull. Chem. SOC. Japan, 1966, 39, 543.
aol G . F. Emerson, K. Ehrlich, W. P. Giering, and P. C. Lauterbur, J . Amer. Chem.
SOC.,1966, 88, 3172.
3 0 8 J. Powell and B. L. Shaw, Chern. Comm., 1966, 323.
J. Powell and B. L. Shaw, Chem. Comm., 1966, 236; J. K. Nicholson, J. Powell,
and B. L. Sha,w, ibid., p. 174.
8 0 4 B. Bogdanovic, H. Bonnemann, and G. Wilko, Angezu. Chm., 1966, 78, 591.
8 0 5 E. J. Corey and H. F. Semmelhack, Tetrahedron Letters, 1966, 6237.
306 R. J. Goodfollow and L. M. Venanzi, J . Chem. Xoc. ( A ) ,1966, 784.
8 0 7 M. S. Lunin. J. Powell. and B. L. Shaw, J. Chem. SOC.(. A.) , 1966, 1687; B. L.
Shrtw, ibid., p. f6S8.
308 A. Zalkin and T. E. Hopkins, Inorg. Chem., 1966, 5, 1189.
M. F. Hawthorne and T. P. Andrews, J. Amer. Chem. SOC.,1965, 87, 2496.
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butadiene compounds [n-(
Ph4C4)Pd(n-BgC2H,,)]and
[z~-(P~*CJP~(~-B~C,H,(CH~),)].~~~
The electron diffraction pattern of ferrocene in the vapour phase indicates
D,,,symmetry for the equilibrium conformation; the CH bonds are bent

away from the plane of the C5 ring by 5" towards the metal.311 The equiva-
lence of the protons of the a-bonded cyclopentadiene group in the n.m.r.
spectrum of the compound (C,H,)Fe(CO),(C5H5)has been investigated by
measuring the spectra over a temperature range and by the determination
of the X-ray structure. The data are interpreted in terms of an intra-
molecular reorientation process.312 The mass spectra of some cyclopenta-
dienyl-metal derivatives 3 l 3 have been obtained, and the nature of the
tetracyanoethylene adducts of ferrocene and cobalocene elucidated.
A new preparation of biscyclopentadienyltitanium(n) has confirmed the
diamagnetism of the c0mplex.3~5 Titanium and zirconium cyclopentadiene
alkylphosphide complexes, [C,H,MPR,], (M = Ti, Zr; R = C2H5 or n-C41Pg)
have been synthesised,"16 and tetrakiscyclopentadienylzirconium was re-
in~estigated.3~7Diphenylketen complexes have been obtained by reaction
of the keten with biscyclopentadienylvanadium and with biscyclopentadienyl
titanium dicarbonyl, respectively, to give [C5H5M(Ph2C=C=O)] (M = Ti, V).
The keten reacts with the metal through the olefin and oxygen groups of
the diphenylketen.3'8 The interaction of the cyclopentadienyl carbonyls of
iron and vanadium with sulphur yields319 the polymeric complexes
[(C,H5),V2S5] and [C5H5FeS],, and whereas cyclohexene sulphide reacts
with the cyclopentadienyl' carbonyl of vanadium 319 to give the same
polymeric vanadium product, the complex [(C5R5)MoS2C,H11],is obtained
from [C,H,MO(CO),],.~~~~ 320 The X-ray structure of the iron adduct has
been 321 The complex C,H,V(acetate), is considered to be a
dimer in the solid, and the magnetic moment ( p = 1.49 B.M.) is indicative
of interaction between the metal ions.322 A series of maleonitrile dithiolate
complexes of some cyclopentadienyl complexes of titanium, molybdenum,
tungsten, iron, and cobalt has been 0bserved;~~3 a related cobalt adduct,
C5H5Co[S,C, (CF,),], 324 has been obtained with (trifluoromethy1)dithione.
310 P. A. Wegner and M. F. Hawthorne, C h m . Comm., 1966, 861.
311 R. K. Bohn and A. Haaland, J . Organometallic Ckem., 1966, 5, 470.
312 M. J. Bennett, F. A. Cotton, A. Davison, J. W. Faller, S. J. Lippard, and S . M.
Morehouse, J . Anier. Chern. SOC.,1965, 88, 4371.
313 F. J. Preston and R. I. Reed, Chent. Comm., 1966, 51; E. Schumacher and R.
Taubenest, Helv. C'lzim. Actn, 1966, 49, 1447.
314 R. L. Brandon, J. H. Osiecki, and A. Ottenborg, J . Orgunometallic Cilem., 1966,
31, 1214.
315 G. W. Watt, L. J. Baye, and F. 0. Drammond, J . Amer. Chent. SOC., 1966,88,1138.
316 K. Issleib and H. Hackert, 2. Naturforsch., 1966, 21b, 519.
317 E. 31. Brainina, M. Rh. Minacheva, and R. Kh. Freidlina, Bull. Acad. Sci.,
U.S.S.R., 1965, 1839.
s l s P . Hong, K. K. Sonogashira, and N. Hagiham, Bull. Chem. SOC.Japan, 1966,
39, 1821.
s19 R. A. Schunn, C. J. Fritchie, and C. T. Prewitt, Inorg. Chem., 1966, 5, 892.
3 2 0 P. M. Treichel and G. R. TVillces, Inorg. Chem., 1966, 5, 1182.
321 C. H. Wei, G. R. Wilkes, P. M. Treichel, and L. F. Dahl, Imorg. Chem., 1966,
5, 900.
322 R. B. King, Inorg. Ch8?n., 1966, 5 , 2231.
s 2 s J. Locket and J. A. McCleverty, Inorg. Chem., 1966, 5 , 1157.
a 2 4 H. W. Baird and B. M. White, J. Amer. Chcwt. SOC., 1966, 88, 4744.
View Article Online
An extensive group of arylazo-derivatives of molybdenum cyclopentadienyl

carbonyl have been prepared, RN,Mo(CO)~(C,H,).~~~ The product of the
reaction of tetraphenylcyclopentadienone with triphenyltin manganese
pentacarbonyl has been reformulated as (tripheny1stannoxy)taphenyl

cyclopentadienylmanganese tricarbonyl.326 The preparation of benzene
cyclopentadienyl manganese(I) and a related series of biphenyl dimeric
species has been described.327,328 Tropylium derivatives have been obtained
from the Friedel-Crafts acetylation of the chromium and manganese cyclo-
pentadienebenzene complexes.328 The compounds C,H,Mo(CO),X, (X = C1,
Br, I) have been obtained by direct halogenation of the cyclopentadienyl-
molybdenum tricarbonyl ~ I i m e r , and
~ , ~ the reaction of the cyclopentadienyl
carbonyl chlorides of iron and tungsten with unidentate nitrogen and phos-
phorus ligands rep0rted.3~0 The electronic and structural similarities o f
cyclopentadienyl-carbonylsand pure carbonyls have been emphasised in the
preparation of the complexes [C,H,Fe( C0)l4 and [C,H,Co(CO)],, and com-
parison with the carbonyls [Co(CO),], and Ru,( CO),,, respectively.331
mCyclopentadieneiron tricarbonyl, (C,H,)Fe( CO),, has been obtained from
cyclopentadiene and iron enneacarbonyl; the compound decomposes at
140" to give the cyclopentadienyliron dicarbonyl dimer.332 Some new
methods for the preparation of alkoxycarbonyl cyclopentadienyl complexes
of iron, manganese, and molybdenum have been de~eloped.~33 The carbon
monoxide insertion reaction of the compound C,H,Fe( CO),CH3, to give
C,H,Fe(CO)(COCH,)L, has been studied with a variety of phosphines
(L),334,335 and the ions [C,H,I?e(CO),L]f are obtained by reaction of the
phosphines with the complexes C,H,Fe(CO),X (X = C1, Br, I).335Stable
monomeric alkyl and aryl mercaptide complexes, C,H,Fe( CO),SR, have
been isolated ; the controlled transformation into pairs of isomeric binuclear
complexes [(RS)Fe(CO)C,H,], has been reported.336 Some alkyl and aryl
trithiocarbonates of iron, [C,H,Fe(CO),CS,R] (R = CH,, C,H,, c6H,), have
been obtained; these lose carbon monoxide in ultraviolet light to yield the
chelated monocarbonyls, [C,H,Fe( CO)CS3R].337 The preparation of the
f i s t trifluorophosphine cyclopentadienyl cobalt complex has been reported,
C,H,CO(PP,),.~~~ The structure of the trimer, [C,H,Rh(CO)],, indicates
a triangular array of rhodium atoms with bridging carbonyl groups and a
cyclopentadienyl group associated with each rhodium atom.339 Dicyclo-
335 R. B.King and H. B. Bisnette, Inorg. Chem., 1966, 5, 300.
326 R.D. Gorsich, J. Organometallic Chem., 1966, 5, 105.
3 2 7 R. G. Denning and R. A. D. Wentworth, J. Amer. Chem. SOC., 1966, 88,4619.
3 2 8 E. 0.Fischer and S. Breitschaft, Chem. Ber., 1966, 99, 2213.
329 R. J. Haines, R. S. Nyholm, and M. H. B. Stiddard,J. Chem. SOC.( A ) ,1966, 1606.
3 3 0 E. 0.Fischer and E. Moser, J. Organometallic Chem., 1966, 5, 63.
331 R. B. King, Inorg. Chem., 1966, 5 , 2227.
3 3 2 R. K. Kochhar and R. Pettit, J. OrganometaZZic Chem., 1966, 6, 272.
5 3 3 R. B. King, M. B. Bisnette, and A. Fronzaglia, J. Organometallic Chem., 1966,
5, 391.
3 3 4 J. P.Bibler and A. Wojcicki, Inorg. Chem., 1966, 5 , 889.
335 P.M.Treichel, R. L. Shubkin, K. W. Barnett, and D. Reichard, Inorg. Chem.,
1966, 5, 1177.
3 3 6 M.Ahmad, R. Bruce, and G. R. Knox, J. Organometallic Chem., 1966, 6, 1.
3 3 7 R. Bruce and 0. R. Knox, J. Organomctallic Chem., 1966, 6, 67.
3 3 8 Th. I<ruck, W, Hieber, and W. Lang, Angew. Chem., 1966, 78, 208.
539 0.S. Mills and E. F. Paulus, Chem. Comm., 1966, 815.
View Article Online
pentadienylrhodium(n), and -iridum(n) have been shown to be paramagnetic
monomers a t liquid-nitrogen temperature and in the gas phase, but to be
diamagnetic dimers at room temperature.340 Base adducts of tricyclo-
pentadienyl complexes of a series of lanthanide elements of the form

(C,H,),M,L (M = Y, Nd, Tb, Ho, Yb, L = cyclohexyl isonitrile; M = Yb,
L = PPh,, OC4H,, NH,) have been 0btained.~~1 The preparation of tri-
cyclopentadienyleuropium 342 and dicyclopentadienylytterbium 343 has been
given.343 The syntheses of the transuranic cyclopentadienyl compounds
(C,H,),NpC1344 and Am(C5H5),345 have also been reported.
Metal-Arene Complexes.-The low-temperature studies of the X-ray
structures of dibenzenechromium favour the symmetry D,, for the mole-
cule.346 The e.s.r. spectrum of the ion [(HMB),Fe]+ (HMB = hexamethyl-
benzene) suggests that the two rings are oblique to each 0ther.~47 The
X-ray structures of (HMB)Cr(CO), and (C6H,)Cr(CO), indicate a staggered
configuration of the rings to the carbon triangle of the carbonyl groups,
whereas in the anisole derivative an eclipsed configurationis observed ;in con-
junction with these results, and from the structure of the (o-toIuidine)Cr(CO),
complex, it is concluded that these effects are related to electronic rather than
steric factors.348 The X-ray structure 349 of 1,6-methanocyclodecapentane-
chromium tricarbonyl prepared recently 350 has been reported, and the
high-field shift of the methylene group is shown not to be associated with
direct metal interaction. The temperature dependence of the proton n.m.r.
spectra of isopropylbenzenechromium tricarbonyl is associated with restricted
rotation of the arene nucleus.351 The X-ray structure of the charge-transfer
complex of (aniso1e)chromium tricarbonyl with 1,3,5-trinitrobenzene has
been 0btained.~5~
The reaction of benzene and methyl-substituted benzene tetracarbonyl
vanadium cations, [(arene)V(CO)4]+, with borohydride to give the z-cyclo-
hexadienyl derivatives has been reported. The n.m.r. and infrared spectra
in the region 2770-2820 cm.-l are assigned to the methylene group and not
metal-hydrogen interaction. 353 The preparation of some cyclopentadienyl-
chromium tropylium cations have been rep0rted,~54and the photochemical
340 E. 0. Fischer and H. Wawersik, J. Organometallic Chem., 1966, 5, 559.
341 E. 0. Fischer and H. Fischer, J. OrganometallicC h . , 1966, 6, 141.
342 M. Tsutsui, T. Takino,and D. Lorenz, 2. Naturforsch., 1966, 216, 1.
343 F. Calderazzo, R. Pappalardo, and S. Losi, J. Inorg. Nuclear Chem., 1966, 28,
987.
3 4 4 E. 0. Fischer, P. Laubereau, F. Baumgartner, and B. Kanellakopulos, J. Organo-
metallic Chern., 1966, 5, 583.
3 4 5 F. Baumgartner, E. 0. Fischer, B. Kanellakopulos, and P. Laubereau, Angew.
Chem., 1966, 78, 112.
3 4 6 E. Keulen and F. Jellinek, J. Organometallic Chem., 1966, 5, 490.
3 4 7 H. Brintzinger, E. Palmes, and R. H. Sands,J . A m . Chem. SOC., 1966, 88, 623.
3 4 8 0. C. Carter, A. T.McPhail, and G. A. Sim, Chem. Comm., 1966, 212.
3 4 9 P. E. Baikie and 0. S. Mills, Chem. Comm., 1966, 683.
3 5 0 E. 0. Fischer, H. Riihle, E. Vogel, and W. Grimme, Angew. Chem., 1966,78, 584.
351 D. E. F. Gracey, W. R. Jackson, W. B. Jennings, S. C. Rennison and R. Sprott,
C h m . Comm., 1966, 231.
3 5 2 0. L. Carter, A. T. McPhail, and G. A. Sim, J . Chem. Soc. ( A ) , 1966, 822; G.
Huttner, E. 0. Fischer, R. D. Fischer, 0. L. Carter, A. T. McPhail, and G. A. Sim,
J . Organometallic Chem., 1966, 6, 288.
353 F. Calderazzo, Inorg. Chenz., 1966, 5, 429.
3 5 4 E. 0. Fischer and S. Breitschaft, Chem. Ber., 1966, 99, 2905.
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substitution of carbonyl groups in arenechromium tricarbonyl complexes

described.355 The reaction of hexamethylbenzene with metal chlorides of
Group IV and V in the presence of aluminium chloride and aluminium powder
gives a series of new n-hexamethylbenzene derivatives, Nb2[(HMB),],Cl,,

[Nb,(HMB),Cl,]CI, [Ta,(HMB),Cl,]Cl, [Ti,(HMB),Cl,]Cl, and
[Zr,(HMB),CI,]Cl. The reduction of dibenzenerhenium cation and the
corresponding hexamethylbenzene complex with sodium in liquid ammonia
yields arene-cyclohexadienyl complexes, but with lithium at 200 Oc reduction
of the metal occurs and a paramagnetic complex [Re(HMB),] is formed; this
has also been converted into a diamagnetic dimer, [Re(HMB),],.357 The
cation [bis-(6,6'-diphenylfulvene)cobalt]
+ has been obtained, and is the first
example of a molecule with two fulvene groups not containing carbonyl
groups.35*
s65 W. Strohmeier, G. Popp, and J. F. Guttenberger, Chem. Ber., 1966, 99, 165.
356 E. 0. Fischer and M. Riihrscheid, J . OrganometaElic Chm., 1966, 8, 53.
967 E. 0.Fischer and H. W. Schmidt, Ber., 1966, 99, 2206.
858 E. 0. Fischer and B. J. Weimann, 2. Naturforsch., 1966, 21b, 84.
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Article in Annual Reports on the Progress of Chemistry · January 1966

Jasmine Lewis John Burgess

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Coordination Chemistry Reviews, ed. A. B. P. Lever, Elsevier, Amsterdam.

2. KINETICS AND MECHANISMS OF INORGANIC REACTIONS

As is usual in these Reports it is only possible to mention a proportion,

A. Haim and N. Sutin, J . Amer. Chem. SOC.,1966, 88, 5343.

taneous two-electron transfer.22 However, kinetics of the vanadium(@-

&11P or &21P mechanisms, never XNlCB.50 Ion-pairing has a marked

are ascribed to enhanced reactivity of ion-~airs.5~ Kinetics and products of

f i s t example of hydroxide catalysis in a square-planar system.62 Pseudo-

differ greatly, implying more complicated mechanisms.72 Results have also

3. THE TYPICAL ELEMENTS,

(a)R. E. Dessy, W. Kitching, and T. Chivers, J . Amer. Chem.Soc., 1966,88,453;

Group 0.-Noble-gas chemistry has been reviewed,6 and noble-gas rad-

contain Xe(m). Raman spectra afford no evidence 25 for the formation of

metallation reactions indicate a9a that organolithium aggregates can act as

kinetically active species ; the extent of aggregation in basic solvents

of ether and to the site of unsaturation in the organic molecule. On

dialkylberylliums to give both 1 : 1 and 1 : 2 complexes

Ph, ,Ph Ph, ,'Ph CH2 - Me2NL

A review of organomagnesium compounds 52a emphasises that the consti-

product, probably with the structure (3). Of the several alkylmagnesium

is determined principally by the atoms directly bound to boron, and (ii)n-

General reviews about B,-B, boron h y d r i d e ~ ,carboranes,

and effective nuclear charge of Z are closely interrelated;75bapplication of

the bridge and terminal hydrogens magnetically equivalent ; the boro-

and probably (HS),BH,- in the thiohydrolysis of LiBH, in tetrahydrofuran

to whether the medium is acid, neutral, or alkaline, respectively. 1lB n.m.r.

81 S . Akerfeldt and M. Hellstrom, Acta. Chem. Scand., 1966, 20, 1418.

B-methylated derivatives of these, and C,3-Me,-1,2-C2B,H3 [see (lo)], the last

Hydroboration of alkynylboranes by alkyldiboranes also affords substituted

91 T. Onak, L. B. Friedman, J. A. Hartsuck, and W. N. Lipscomb, J . Amer. Chm.

attached, respectively, to adjacent C, C, and B atoms of the open face.lO7a In

viz. ,X2C2BgHIl,are also formed by alcoholic cleavage of CC‘-dihalogeno-

carboxylic acids,l1* alcohols, 3d amines, 11%halides,llgf ketones,ll3g and

[Reproduced from M. F. Hawthorne and R.L.Pilling, J . Amer. Chem. Soc.,1966,:88,

the status of certain fluoroborates, the interrelationship of the four primary

n-Bonding in aminoboranes has been the subject of molecular orbital cal-

~ ~ 5 ~ studies of which indicate the sequence

appeared. Convenient syntheses of boroxine lPgU and trimethylboroxine 14gb

azides (Et2AlN3)lSgbare also associated under normal conditions, with

0yo- Si,R3 MeZSi

by the vibrational spectra of alkaline aluminate solution^,^^^ the one pre-

species built up from &(OH), octahedra.

ionic (e.g. [T1(pyridine),C1,]+~Cl4]-)structures for these and similar com-

been confirmed.104 In SiF,, the microwave spectrum leads to a bond anglelO5Q

radical, generated by the thermal decomposition of (Me,Si),Hg, extracts

formed.206a Triphenylsilyl-lithium reacts with chloro-N-dialkylamino-

Ph2Si -SiPhz Ph S'- SiPhz

The compound (22) reacts with lithium followed by QC1, (Q = S, PhP,

reacts 217 with Si2C1, to form (Me,N),Si2; the compound Ph,SXElCl is

the structures of the isomeric hydrazine derivatives (Me,Si),N,H, have been

The formation and reactions of Si-P compounds have been discussed;Is1

Me2AuBrto give 2~ Me,SiOAUMe,. Silanols react 227a with perfluoracetone,

( a )J. Dahlmann, A. Rieche, and L. Austenat, Angew. Chem., Internat. Edn.,

m e t ~ y The ~ of an electric discharge on a mixture of GeH,, SiH,, and

midal. Compounds containing Ge bound to Sn or Pb have been obtained

react with gallium alkyls to give 181b dimeric R,GeOGaR,. Triphenylgermyl