Kinetics and mechanisms of the oxidation of ascorbic acid and benzene diols by

nickel(III)tetraazamacrocycles in aqueous perchloric acid

A . MCAULEY,'T. OSWALD,'A N D R . 1. HAINES
Deprvrrner~rqf Chernisrrp, Ur~iver-sir! rf Vic.tor.irr, Vic.tor.irr, B .C. , Crrr1rrrlrr V 8 W 2 Y2
Rcccivcd Fcbruary 12, 1982.'

A. MCAULEY, T. OSWALD.and R. I . HAINES. Can. J . Chem. 61. 1120 (1983).

The kinctics of rcaction of ascorbic acid, hydroquinone. and catcchol (H2A) with nickel(lll) mncrocycles (NiL3')
(L = cyclam, rneso-(5,12)-7,7,14,14-Mc,,- 14-anc- I .4.8.1 1-N, (tct-rr). and r-r1~~-(5.14)-7.7.12.12-Mc,,-
14-anc- I ,4,8,1 1-N,
(tet-c):

have been invcstigated in aqueous perchloric acid solutions using thc stoppcd-flow technique. The data arc consistent with a
ratc-determining one-electron transfer reactions:

k'
NiL" + HA- + NiLzf + HA
H,A HA- + Hf (K;,)
followed by a rapid oxidation of thc radical formed. In thc reaction with ascorbic acid, for Ni(cyclarn)". kl = 250 M - ' s-'
(25"C), k4K,, = 680 s - ' ; Ni(tet-c,)'+, k, = 2.52 x 10' M - ' s - ' , LK., = 1.06 x 10' s - ' ; and Ni(tet-r~)~',k, = 2.85
x lo3 M - ' s - ' (21.95"C), k4K., = 1.26 x l o ' s - ' . With catcchol, kl = 6.98 x 10' M - ' s - ' , 1.73 x 10' M - ' s - ' . and
3.3 X 10' M - ' s - ' respectively in reactions with ~ i ( c y c l a m ) ' ~Ni(tct-c)>',
. and Ni(tct-r~)~'.With hydroquinone, kl = 1.09
X 10' M - ' s - ' (Ni(cyclam)") and 2.49 X 1 0M - ' s - ' (20.9"C) (Ni(tet-c)."). The reactions are considered to take place via
an outer-sphere mechanism and rate constants are discussed in terms of the Marcus cross correlation. Use has been made of
predicted rate constants to identify reaction pathways in the hydrogen-ion dependcnt systems.

A. MCAULEY. T . OSWALD et R. 1. HAINES. Can. J . Chem. 61, 1 I20 (1983).

Faisant appcl i la mCthode de flux steppe. on a ttudie, dans dcs solutions aqueuses d'acide perchlorique, la cinktique de
la rtaction de I'acide ascorbique, de I'hydroquinone et du catCchol (HZA) avec les macrocycles de Ni(ll1) (NIL'')
(L = cyclam, ~116.ro-(5,12)-7,7,14.14-Me,-ane- 1 4 - N , - 1 4 8 I I (tit-rr) et r-rrc-(5.14)-7,7,12.12-Mc(,-ane-14-N1-l ,4,8, I I
(tCt-c):

Lcs donnees s'accordent avec une 6tape de transition impliquant dcs reactions de transfert i un electron:

k'
NiL3+ + HA- + NiL'+ + HA'
H'A HA- + H' (K;,)
qui serait suivi par une oxidation rapide du radical form6 lors dc la reaction de I'acide ascorbique avec le Ni(cyclam)'+,
k, = 250 M - ' s - ' (25°C). k,K,, = 680 s - ' ; avec Ni(t6t-c)'+ kl = 2,52 x 1 0 ' M ' s ' . k4K., = 1.06 X lo's-' et Ni(t6t-(I)'+.
k, = 2,85 x 10.' M - ' s - ' (21,95"C), k'K;, = 1,26 x 10' s-'; dans le cas du catechol. ces valcurs sont respectivement
k, = 6.98 x 10' M - ' s - ' ; 1,73 X 10' M - - ' s - ' et 3,3 X 10' M ' s-I pour Ics reactions avec le Ni(cyclam)", Ni(tCt-c,)" et
Ni(tCt-a)"+;avec I'hydroquinonc kl = 1.09 X 1 0 ' M ' s-I (Ni(cyclam)") et 2.49 X 105M - ' s - ' (20,9"C) (Ni(t6t-c,)"). On
considtre que ces reactions se font via un mecanisme hors sphtrc ct on discute dcs constantes de vitcsse cn fonction de la
corrklation croisCe de Marcus. Dans lcs systkmcs oh il cxiste unc intlucncc dcs ions hydrogenes on a utilisk les constantes dc
vitesse prCvucs pour identifier les schtmas dc rtactions.
[Traduit par le journal]

Introduction both inner- and outer-sphere redox behaviour. Intermediate

A variety of metal complexes have been studied as oxidants
(1 -7) in reaction with ascorbic acid and there is evidence for
'To whom all correspondence should be addressed.
'present address: Department of Chemistry, University of Calgary,
Calgary, Alta., Canada T2N IN4.
Revision received November 9, 1982.
complexes have been identified in the reactions with vana-
dium(V) (8) and aquo-iron(ll1) (9) where the redox process
involves the formation of an ascorbate radical ion rather than a
two-electron transfer to yield the dehydroascorbic acid. A m o n g
other for example, the reaction of
tris(phenanthroline)iron(III) and its derivatives (2), and the re-
actions involving thioureapentacyanoferrate(lll) (10), the dif-
 ET AL. 1121

ferences in oxidation rates have been discussed in ternis of free

energy changes as related to the Marcus theory ( I I).
In previous studies from our laboratory, we have inves-
tigated redox reactions of nickel(lI1) niacrocyclic complexes.
Complex forniation has been observed in the reactions of
nickel(ll1) cyclam (cyclam = 1,4,8,1 I-tetraazacyclotetradec-
ane) with C1-, Br-, and NCS- (12) but with I (12) and aro-
matic diols (13) a redox process occurs. These nickel(1Il) mac-
rocycles with various ring substituents offer a wide range of
oxidising potentials, but relatively few studies have been made
of the kinetics and mechanisms of reactions with reducing
substrates. In the present paper we report the results of a kinetic
study of the oxidation of ascorbic acid by Ni(11l)L" ( L
= cyclam, tet-a, and tet-c.), and of the latter two complexes as
oxidants in reactions with hydroquinone and catechol.

Experimental
Nickcl(l1)L" ( L = cyclam, tet-a, tet-c.) were prepared as de-
scribed in the literature ( 14). Cyclam (Strem) was recrystallised from
ethanol before use. For thc latter two complexes. the Me,-4. I I - and
Me(,-4,14-N, diene intermediates prepared initially were reduced to
tet-[I and tet-c. rcspeetively using Ni/AI alloy at 70°C. Solid samples
of the Ni(lll) complexes NiL(CH.JCN)Z.(ClOa)rwere prepared by elec-
trolysis (0.01 M NaCIO,) of the corresponding Ni(ll) species in rig-
orously anhyd1.0~~ acetonitrile (P20S/CaH2)at 5°C in the dark under
dry N,. Thc solids were stored at - 15°C in the dark.
L-Ascorbic acid was used as received (Sigma) while cateeliol and
hydroquinone were reerystallised from ethanol. LiCIO, was prepared
by neutralisation of Li,C03 with HClO, and recrystallised three times
from distilled water. Care was taken to ensure the absence of SO,'- FIG. 1. First order substrate dependence: k,,,,, vs. [reductant].
ion, which was removed by adding a slight excess of Ba(CIO,),. + + ascorbic acid, T = 25°C.
( A ) ~ i t e t - c z + catechol, ( B ) ~itet-c."
The stopped-flow apparatus and data acquisition system used have HCIO, = l .OO M.
been dcscribed previously (15). For some runs a modified Applied
I Photophysics instrument was used. Both reservoirs and the drive the observed rate constant, kob,, on reductant concentration
1 syringes were therrnostatted by circulating water (controlled to (Fig. I).
: '0.05"C). Absorbance data were collected at desired time intervals
1 and processed using a PCM 12 minicomputer. In general, for each Renctiotz with c~scorbic~zcill
!
run, 200 points were used and rate constants quoted are the least Hydrogen ion dependences of the rates were investigated for
, squares slopes of log (OD, - OD,) vs. time curves. each oxidant. Although solutions of Ni(l1l) cyclam were suf-
Solutions were prepared immediately before starting the cxperi- ficiently stable at pH 2 for kinetic measurements to be made,
ments. which were carried out with an excess of reductant. Ionic owing to the limited stabiIity with respect to intramolecular
strength ( I .O M ) was maintained constant with LiCIO,. Solutions of decomposition of the tet-n and tet-c complexes at [H']
Ni(lll)p' (L = tet-(1, tet-c,) were prepared by adding the required
. .' ,

amount of solid to the therrnostatted solution immediately prior to

< 0.2 M, hydrogen ion dependences for these species were
reaction. This is especially important at lower acid concentrations studied over the range 0.2- 1 .OM. Investigations were carried
where decomposition of the (N~L") in the absence of reductant was out in the temperature range = 5.1-3 l.I°C. For all three
complete in 10- 15 min. The disappearance of Ni(lIl)eyelamz' was oxidants the rate of reaction was observed to be inversely
observed at 380 nm and that of Ni(III)L3' (L = tet-(I, tet-c.) at dependent on [H'] with linear plots of the second order rate
408 nm, yielding pseudo-first order plots which were linear over at constant, kz (= k,,h,/2[H,A]) against [Ht]-' showing positive
least three half-lives. intercepts (Fig. 2).
These data are consistent with reaction of nickel(111) species
Results and discussion with neutral and anionic forms of the ascorbic acid.
Spectrophotometric titration of the ascorbic acid and of the [2] HZA S H' + HA- (K,)
diols w ~ t hthe nickel complexes showed a stoichiometry of
2.0 mol of nickel(l11) reacting per mole of reductant within k
experimental error ( 2 4 % ) . The overall reaction may thus be [3] ~ i ( l l 1 ) ~+
" H'A 4 NI(II)L'' + (HA' + H')
written as
[I] ZNi(111)~" + H2A + 2 ~ i ( l l ) L " + A + 2H' [4] Ni(111)~" + HA- 3 Ni(11)L2' + (AB- + H')
followed by rapid oxidation of the radical intermediate

-
where L = cyclani, tet-n, tet-c, and H,A = ascorbic acid, cat-
echol, or hydroquinone and A is dehydroascorbic acid or the
fast
corresponding quinone. [5] Ni(111)~" + A'(HA') N ~ ( I I ) L "+ A(+H')
At constant [Ht], the reactions were first order with respect
to both oxidant and reductant as indicated by the pseudo first- An alternative mechanism, involving two-electron transfer
order disappearance of Ni(II1)L" and the linear dependence of reactions,
1122 CAN J . CHEM. VOL. 51. 1'18.3

TABLEI. Ratc constants for reactions of ascorbic acid with Ni(1ll)

macrocyclcs, I = 1.00 M (HClO.,/LiCIO.,)

Ni(lll)cyclam'+ 1 1.5 0.15

19.0 0.18
25.0 0.25
30.1 0.3 1
AH' = 6.5 t 0.8"
A s = = -25.7 ? 5"
Ni(1ll)tct-c" 5.1 0.409
10.1 0.72
14.7 1.01
19.8 1.83
25.2 2.52
A H - = 14.4 2 1 . 1 "
A S = = 10.0 i 4"
Ni(lll)tct-n" 9.6 1.47
15.0 I .76
18.9 2.14
21.9 2.85
AH' = 7.9 ? 1.7"
I I I t t AS7 = - l l , 4 ? 5 "
2.0 4.0 [,+f1-1/ M-l
"In kcal m o l - I .
"In cal deg ' m o l - I
FIG 2. Dcpcndencc of k, on [H'] and tcmpcrature. Reaction of
Ni tet-c" with ascorbic acid

N~(III)L" + H,A + Ni(I)LH' A + 3HH' 2(k, ' 1'

+ ( h K , + k,K,,)/[H '1) [N~(~~~)II,,,[H,A]I,~I[H

Since measurements were made in the range [HI] = 0.1-

is also consistent with the observed data. There is. however, no
evidence for any concerted two-electron reduction of nickel-
(111). The redox potential for the couple
has been determined as +0.39 V (30°C) in I M acid (16). For
the reduction
in DMF, E" = - 1.295 V (170). Assuming a similar value in
aqueous media, when combined with the reduction potential
(1.23 V ) for ~ i " ' ~(17b),
" the overall Ni(III)L/Ni(I)L potential
may be estimated at --0.05 V, effectively ruling out any
two-electron process. Using the data of Busch et al. (18), the
~ i l l l / l potential is --0.70 V (in CH,CN versus a Ag/Agt
(0. I M ) reference electrode).
Although the reaction of the H,A species (reaction [3]) may
be assigned uniquely, there persists a "proton ambiguity" in the
case of [4] since an equivalent representation, [7], may be
presented:
k
[7] ~ i ( l l l ) ~ ( O+~H,A
) ' ~2 Ni(ll)L2' + HA'
There is evidence (19) for a pentacoordinate geometry of the
hydroxo species for the tet-a and tet-c complexes whereas the
-
cyclam complex has been shown (at pH 10) to exist in the
form N~L(oH);.
Using the reactions [3], [4], and [7] together with the associ-
ated equilibria, the rate expression is of the form
l.OM and K , -
10-'M ( I , 4 , 20) and K,, 10-'M (13, 21),-
the second order rate constant may be written as
[9I k? = k~ + ( ~ J K+, k7K1,)/[HtI
consistent with the experimental observations. There is no ev-
idence for any [H 'I-' dependence attributable to the reaction of
HA- with [Ni(III)L(OH)]" which may be expected at higher
pH's. Rate data are shown in Table I.
Nickel(I11) species have been shown to form complexes with
sulphate ions (21, 22). The reduction potentials associated with
these systems are lower (by -300 mV) than those for the aquo
ions. We have examined the effect of sulphate on the reaction
rates and find a marked decrease attributed to slower reactions
of the sulphato complexes (Table 2). A similar effect has been
observed previously in reactions of benzene diols (13) and in
sulphate media an evaluation of the data based on reactions of
nickel sulphate complexes as oxidants has been presented. In
the present system, however, although the data are consistent
with only monosulphato complexes reacting (as observed from
the linear dependence of k,-I against [SO,'-],), the changes in
rate with [H'] could not be assigned unambiguously and no
extensive studies were therefore carried out.
Reactiorzs with catechol and hydroy~tirlorle
Previous studies in these laboratories have dealt with the
oxidation of these substrates by a variety of reagents ( 1 , 13). In
the present investigation we have extended the data on Ni(ll1)
reactants to include the tet-a and tet-c complexes. Studies have
been made at [H'] = 1 .OO M in order to limit reaction to only
the Ni(lll)L3+oxidant. In the range [H'] = 0.1 - 1 .OO M for
reaction of these reductants, there is a fairly constant rate ob-
 TABLE2. Effcct of sulphatc ion on thc ratc of oxidation of
ascorbic acid by ~ i ( l l l ) c ~ c l a m ' (in
+ all cxpcrinicnts.
[~i(lll)cyclam~'] 5 x - M, ascorbic acid = 5.0
x lo-" M )
T/"C [H'IIM [SO"'-I,/M k,/M1 s ' The second order rate constant may be expressed in the form

k , l values are presented in Table 3. The first order dependence

of the rate on [H,Q] is shown in Fig. I ( T = 25.6"C) and the
other data quoted are the mean values of constants derived
using at least two differing reductant concentrations. In the
reaction of Ni(ll1)tet-a" with hydroquinone, however, the rate
was too rapid to be observed in our apparatus. (Using solutions
of 5 X lo-' M [H,Q] and 5 X lo-" M [Ni(lll)], [H']
= l.OOM, T = 25"C, tllz -
3 ms.)
Although attempts were made to identify intermediate com-
plexes formed, there is no evidence in any of the systems
TABLE^. Ratc constants for reaction of Ni(l1l)- studied for axially coordinated precursors, suggesting an outer-
tct-(1" and ~i(lll)-tct-c."complcxes with catcchol sphere mechanism.
and hydroquinone, (H'] = l .OO M, I = l .OO M" The Marcus theory ( 1 I ) affords the possibility of correlating
((I) Ni(l1l)tct-c,'+ free energy changes with the rate data, and its applicability to
redox reactions involving organic substrates has been verified
in the case of ascorbic acid (3, 10) and q ~ ~ i n o (l sI , 24, 25)
oxidised by a variety of Ir(lV), Fe(llI), and Co(ll1) ions. The
Catechol relationship may be expressed in the form
5.90 0.84X lo"
11.61 1 . 0 1lo'
~
16.00 1.18~10"
20.90 1.35X 10" where^^: = AG;? + M J ~ ? - w I ,A = ~ ( A G ,-] II:~!:.+ AG;
25.60 1.73X lo" - w??), and k I 2= Z ~ X P ( - A C ; ' S / R T )AGE . and A G a r e f r e e
AH* = 5.4 *
1.2 kcal mol-' energies of activation of the self-exchange process and wl and
AS' = -21 *
8 cal deg-' mol-' w,, represent the associated work terms involved. rv,, and I V ~ ,
Hydroquinone are the work terms required to bring together the reactants or
1 I .61 1.18~10~ products in the activated complex (26. 27). In many of the
16.00 1.30X lo5 systems under study. since one of the reactants (or products) is
20.90 2.49 X 1 O5 uncharged, work terms are considered to reduce to zero.
The free energy of activation for the self-exchange process
for ~ i ( c ~ c l a m ) ' + / ' +
has been measured recently (13. 28). Both
direct measurements involving esr and cross reactions with
F~(LL):' yield a value of AG:) = 10.9 2 1.0 kcal mol-I.
Catechol There are no experimental data available for the self-exchange
25 3.30X 10" rates for H2Q/H,Q' or for H,A/H,At. Estimates for the
AG:I: = 8.84 kcal mol-'I' quinols have been made from cross reactions with I ~ C I and ~-
MO(CN);-, however, with a value in the range AG: - 6-7
"Rate constants corrected for protonated rcductant present kcal mol-I (29). We have used a value of ACT,'"= 6.0 kcaI
under these reaction conditions.
" ~ s s u m i nk ~= IO"e-I" ' ' I . mol-' ( k , , -4 x lo6 M - I s-I). The con~plexitiesof ascorbate
as a reductant have been described recently (30). From an
served with a small, reproducible retardation in rate becoming analysis of emf data derived for the A ' / A ' couple (31), a
increasingly more pronounced in the range [H '1 2 0.6 M. This value for EU(HA'/HA-) = 0.68 V has been proposed, some-
is attributable to the protonation of the organic substrate, what lower than that suggested previously. Using data for the
reaction with F ~ ( L L ) ; ' ,the self-exchange rate for the reaction
is calculated as 10'- 10"M-' s-I, consistent with that (10'M-'
s-I) derived from the Fel"(cyt-c)/HA- reaction (32). It is con-
where HzQ represents the quinol. Values of K l o have been sidered that barriers to the electron exchange process derive
shown to lie in the range I - I0 M for alcohols with the constant from differences in C=C and possibly C-C bond lengths in
K l o = 3.9 M for phenol (23). In the case of hydroquinone and the various species. 'The data for H,A/H?A' are more tentative,
catechol, values of 4.5 2 1.2 M and 3.3 2 0.9 M have been however, owing to a lack of a measured value for the second
determined from kinetic measurements, and interpolation into pK, of the ascorbate radical ( H 2 A i HA' + H-'). Since the
the data of Pelizzetti (24) on the oxidation of catechol by 1 r ~ l ; - value for pK;,, (HA' $ H' + A') is negative (-0.45), using
is consistent with K l o = 5.3 2 2 M for this species. At the data of Steeken and Neta (3 1) for the one-electron potentials
[H+] = 1 .OO M some of the reductant will be in the protonated E'(A;/A'-) at higher pH's (1 1, 13.5), an approximate value
form. There is no evidence from any study to date of H,Q' for E o ( H 2 ~ / ~ ? Amay ' ) be calculated from known pK's and an
reacting. Assuming only H2Q to react, assumed value of pKa2. If pKaz lies in the range - 1 to -4,
1124 C A N . J . CHEM. VOL. 61. 1983

TABLE
4. Compar~sonof calculatcd and cxpcrimcntal data
*G""
Reaction *G 121,,,,\,~' Q" " k, ,,,I' LC.,,,"
' + HZA
+ H'cat
+ H2Quin
+ HA-

"kcal mol-'.
"M-Is-'.
'Assuming no contribution from reaction [7], work term contr~butionincluded in evaluation of Q
"See eq. [15].
"Reference 13.

ment is consistent with an outer-sphere designation for these

Q oxidations.
kcal rnol-' "
Adherence to the Marcus treatment enables some predictions
-2 /" to be made with respect to the relative rates of the hydrogen
d e 3
ion dependent pathways for ascorbic acid. Using AG?,
= 9.55 kcal mol-' (Eo = 0.68 V), the rate constants for the
process NiL" + HA- (k4) may be calculated (Table 4). In the
1 -12 -10 -8 -6 -L /6
. 2 4 6
/:" -.2 ~6~
kcal rnol-' reaction of ~ i ( c ~ c 1 a m ) with
" HA-, for example, k,(calcd.)

/
7.
--'
--6
-8
8 1
FIG.3. Plot of Q against AG:, eq. [I51 for various systems. The
numbers refer to reactions indicated in Table 4.
E'(H2A/H2Ai.) = 0.98 + 0.10 V. The rate of oxidation of
H2A by F~(LL):' (LL = 1,lO-phenanthroline) has been mea-
sured recently (33) and from the observed rate (1.73 x lo5M - '
s-I) a self-exchange rate for H2A/H2At of -10' M-I s - ' may
be derived. We have used these data in our calculations. In the
case of ~ i ( t e t - c ) ~ ' . / "and ~i(tet-a)"/" we observed reason-
able agreement with systems studied using a value A G , ~ " been presented on the formation of nickel(I11) complexes with
= 14.0 kcal mol-' ( k l , - 2 M - ' s-I). Differences in AGYl
have been observed previously with changes in ligand structure
for the corresponding cobalt(lll) complexes (34).
In Table 4 , comparison is made of the calculated rate con-
stants and those derived experimentally. In most cases the
agreement is good when uncertainties in the self-exchange rates
(- 1 kcal mol-') are taken into account. Rearrangement of [14]
leads to the expression
= 1.3 x lo6 M - ' s-'. The composite constant observed,
(k,K, + k7K,) = 6.8 x 10' M - ' s-I. If only the k4 path is
significant, using K, = 1.09 x lo4 M ( l o ) , k,,, (= 6.2
x 10' M-I S - I ) in reasonable agreement with the predicted
value. It is known (35) that Ni(lll)L(OH)" is a weakeroxidant
than Ni(llI)L"+ so that the former species may be predicted to
be less reactive. Also if the hydroxo species are penta-
coordinated as seems likely, then an inner-sphere route may be
a possibility in this instance. The hydrogen ion dependence of
the reactions with ascorbic acid is therefore attributed to HA-
as the reducing ion. There are, in fact, very few instances
where only the H?A pathway predominates (36).
Further studies on redox reactions involving series of organic
substrates such as those under consideration will be useful in
providing a deeper insight into the use of the Marcus theory in
the description of rate processes involved. Recently, data have
a variety of polydentate (N4 and N,) macrocyclic ligands (37).
Studies of the rates of redox reactions involving such species
will be helpful in identifying contributions deriving from ligand
effects on the metal centre. It is also inferred from the present
study that significant changes in the rates of self-exchange
reactions for the N ~ L " / ' ~ couples occur with ligand substi-
tution. Electron spin resonance studies are planned to attempt
to obtain a direct measure of these effects.

Acknowledgements
and in Fig. 3 is shown a plot of AG: against Q. The least- We thank the Natural Sciences and Engineering Research
squares slope (0.57) and intercept (0.03) are close to those Council of Canada and the University of Victoria for financial
predicted theoretically, with only the values for reaction of support. Helpful discussions with Drs. D. H. Macartney and
Ni(tet-c)" and Ni(tet-a)" with ascorbate ion (not included in J. M. Winfield are acknowledged.
the least-squares treatment) showing significant deviations. In
these systems, however, very large free energy changes are 1. Z. AMJAD,
J . C. BRODOVITCH, and A. MCAULEY.
Can. J . Chem.
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and E. PRAMAURO.
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 McAULEY ET AL. 1125

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