Chemistry 3820 Answers to Assignment #3

Topic: Basic coordination chemistry. You are responsible for Ch. 7 (Ch. 6 in the 2nd edition).

1. Without using reference material, write out the 3d elements in their arrangements in the periodic table. Indicate the metal
ions that commonly form tetrahedral complexes of formula [MX4]2 where X is a halide ion.

3 4 5 6 7 8 9 10 11 12
44.9559 47.88 50.9415 51.9961 54.9380 55.847 58.9332 58.693 63.546 65.39
Sc Ti V Cr Mn Fe Co Ni Cu Zn
21 22 23 24 25 26 27 28 29 30

Td Td Td Td Td

2. On a chart of the d-block elements created in question #1, identify the elements and associated oxidation numbers that
form square planar complexes. Give formulas for three examples of such complexes.

The square-planar geometry is primarily associated with the d8 electron configuration, and the following elements and
oxidation states commonly form the d8 configuration:

3 4 5 6 7 8 9 10 11 12
Ni2+

Rh+ Pd2+
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Ir+ Pt Au3+

Examples of such complexes: RhCl(PPh3)3, IrCl(CO)(PPh3)2, Ni(CN)42, PdCl42, cis- and trans-PtCl2(NH3)2 and AuCl42.
Note however that NiCl42 is not square planar, but is instead tetrahedral. In general, the preference for square planar vs.
tetrahedral increases with increasing ligand field strength; the ligand fields for the 2nd and 3rd transition series are
intrinsically larger than for the first series metals. Note however, that Ni(CO)4 is also tetrahedral, not square planar, but
that is because this complex is d10, rather than d8!

3. a) Sketch the two structures that describe most six-coordinate complexes. Which is more common?
b) Give formulas for three different complexes that have the more common six-coordinate structure.

octahedral L L trigonal prismatic

a) L L
L L
M M
L L
L L L
L

Trigonal prismatic is an extremely rare geometry, but octahedral is extremely common.

b) Some common examples of six-coordinate complexes are [Cr(NH3)6]3+, [Cr(CO)6], [Cr(OH2)6]2+, [Fe(CN)6]3,
[Fe(CN)6]4, and [RhCl6]3. In addition, almost all metal aqua ions (save only Cu2 in the first TM series) have octahedral
aqua complexes in water or dilute acid.

4. Name and draw structures of the following complexes: (a) [Ni(CO)4]; (b) [Ni(CN)4]2; (c) [CoCl4]2; (d) [Ni(NH3)6]2+.

2- NH3 2+
CO Cl
CO NC CN 2- Cl NH3 NH3
Ni Ni Co NH3 Ni NH3
CO NC CN Cl

CO Cl NH3

tetracarbonylnickel(0) tetracyanonickelate(2-) tetrachlorocobaltate(2-) hexaamminenickel(II)

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5. Draw the structures of representative complexes that contain the ligands (a) en, (b) ox2, (c) phen, (d) EDTA4.

Here it is best to use HyperChem. The complexes I have chosen to draw are listed below the structures. I used the model
builder cautiously and then MM+ under the Molecular Mechanics method to minimize the structures. Notice the
differences between the saturated ligands en and EDTA and the unsaturated (-bonded) ligands ox and phen. This leads
to puckered rings for the saturated ligands, while the unsaturated ligands are planar.

(a) [NiCl4(en)]2 (b) [Ni(NH3)4(ox)]

(c) [NiCl4(phen)]2 (d) [Ni(EDTA)]2+

6. Draw the structure of (a) a typical square-planar four coordinate complex; (b) a typical trigonal prismatic six-
coordinate complex; (c) a typical complex of coordination number 2. Name each complex.

(a) [Ni(CN)4]2 tetracycanonickelate(II) (b) [Mo(S2C(CN)2] tris(maleonitriledithiolato)rhenium(0)

(c) [Au(CN)2]2 dicyanoaurate(I)

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7. Give formulas for (a) pentaamminechlorocobalt(III) chloride; (b) hexaaquairon(3+) nitrate; (c) cis-
dichlorobis(ethylenediamine)ruthenium(II); (d) -hydroxobis[pentaamminechromium(III)] chloride.

(a) [CoCl(NH3)5]Cl2 (b) [Fe(OH2)6](NO3)3 (c) cis-[RuCl2(en)2] (d) [(NH3)5Cr(-OH)Cr(NH3)5]Cl5

The key in these questions is to identify the ligands and their charges: ammine = NH3, neutral, chloro = Cl, aqua = H2O,
neutral, ethylenediamine = en = H2NCH2CH2NH2, neutral, hydroxo = OH. Then include the oxidation state of the metal,
compute the charge on the complex (note: use square brackets to identify coordination complexes!), and then
compensate the charge by the appropriate number of counterions. Note that convention does not specify how many
counterions are to be included. All chemists accept the need to figure this out by the method described above.

8. Name the octahedral complex ions (a) cis-[CrCl2(NH3)4]+; (b) trans-[Cr(NCS)4(NH3)2]; (c) [Co(C2O4)(en)2]+. Is the
oxalato comples cis or trans?

(a) cis-tetramminedichlorochromium(III); (b) trans-diamminetetraisothiocyanatochromate(III);

(c) bis(ethylenediamine)oxalatocobalt(III)

This question works similarly to #7, but you operate backwards. In this case, we need to determine the oxidation states
of the metal from the overall charge on the coordination complex, indicated by the square brackets, and from knowing
the charges on the ligands. The ligands in this question that are not in #7 are NCS, thiocyanate and C2O42, oxalate.
Note that all anionic ligands are modified to end in o. Ligands are arranged in alphabetic order by the first letter of
the ligand, indicated in bold in the names above (you should not label these as bold in your answers!) Note the mm
in the name for ammonia, but a single m in the organic amine ligands. Also note the use of tris to indicate three,
rather than tri, because there is already a number specification built into the name of the ligand.

9. Draw all possible isomers of (a) octahedral [RuCl2(NH3)4]; (b) square-planar [IrH(CO)(PR3)2]; (c) tetrahedral
[CoCl3(OH2)]; (d) octahedral [IrCl3(PEt3)3]; (e) octahedral [CoCl2(en)(NH3)2]+.

(a) trans and cis [RuCl2(NH3)4]

(b) trans and cis [IrH(CO)(PMe3)2] (I chose R = Me for simplicity)

The designations cis and trans mean the same thing in square planar and octahedral complexes (as in organic chemistry),
and stand for at the same side and opposite, respectively (these are both Latin prepositions in common use in that
language).

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 (c) [CoCl3(OH2)] (one isomer)

d) mer and fac [IrCl3(PMe3)3] (I chose R = Me for simplicity)

Here mer is short for meridional, the name given to the arrangement of groups in the structure shown at left, while fac
stands for facial, the name given to the arrangement of groups in the right hand structure.

(e) [CoCl2(en)(NH3)2]+
There are not unique names for these three complexes. At top left, the two chloride ligands cis to each other and the
ammines are trans to each other. Top right has the two chloride ligands trans to each other, but the ammines cis. In the
bottom isomer, each chloride is trans to an ammine.

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10. The compound Na2IrCl6 reacts with triphenylphosphine in diethylene glycol under an atmosphere of CO to give trans-
[IrCl(CO)(PPh3)2], known as Vaskas compound. Excess CO produces a five-coordinate species and treatment with
NaBH4 in ethanol gives [IrH(CO)2(PPh3)2]. Draw and name the three complexes.

PPh3 PPh3 PPh3

CO CO
Cl Ir CO Cl Ir H Ir
CO CO
PPh3 PPh3 PPh3
Names, in oder: Carbonylchlorobis(triphenylphosphine)iridium(I) Dicarbonylchlorobis(triphenylphosphine)iridium(I)
Carbonylhydridobis(triphenylphosphine)iridium(I)

11. Which of the following complexes are chiral? (a) [Cr(ox)3]3; (b) cis-[PtCl2(en)]; (c) cis-[RhCl2(NH3)4]+; (d)
[Ru(bipy)3]4+; (e) [Co(edta)]; (f) fac-[Co(NO2)3(dien)]; (g) mer-[Co(NO2)3(dien)]. Draw the enantiomers of the
complexes identified as chiral and identify the plane of symmetry in the structures of the achiral complexes.

(a) [Cr(ox)3]3 It is definitely chiral; two chelating ligands on an octahedral framework are sufficient do impart chirality to
the complex. The two enantiomers are shown below (i.e. left and right of a plane of reflection).

(b) cis-[PtCl2(en)] This molecule would be chiral because of the twist in the en ligands, as shown in the two structures
below shown as their mirror images. However, ring inversion in chelate complexes of this type (as in cyclopentane) is
very fast at room temperature and well below, so that enantiomers cannot be isolated, and the complex is normally
considered to be achiral.

(c) cis-[RhCl2(NH3)4]+ This complex is achiral. It has C2v

symmetry, and thus has two internal mirror planes, which can be
clearly seen in the picture of the molecule, one virtical and one
horizontal to the page. Note that the symmetry requires the
ammine ligands to be in a specific orientation. In practice, the
RhN bonds rotate sufficiently fast that the ammine ligands are
effectively spherical, so the molecule definitely acts as a C2v
species.

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(d) [Ru(bipy)3]4+ This is another example of a tris chelate complex, and therefore will be both chiral and easily resolvable.
The stucture is shown with its non-superimposible mirror image below (H atoms omitted for clarity).

(e) [Co(edta)] When EDTA chelates a metal such that all six donor atoms coordinate (the most common, but not the only
way that this ligand attaches to metals) then the resulting complexes are chiral. The non-superimposable mirror images are
shown below.

(f) fac-[Co(NO2)3(dien)] (note typo in question!) and (g) mer-[Co(NO2)3(dien)] (note typo in question!). These two
isomers are shown below at left and right, respectively. If one ignores the conformations of the chelate rings, the
complexes are not chiral. The chelates are ethylenediamine linkages, and as discussed for (b) above, such rings
interconvert too rapidly to allow the separation of enantiomers of these complexes. The facial isomer has an internal plane
of symmetry that includes the central N of dien, the metal and one of the nitro groups. The meridional isomer has a plane
through the dien ligand and the metal (as well as one through the metal and the three nitro N atoms.) These planes are
vertical to the paper through the middle of the molecules.

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12. One pink solid has the formula CoCl35NH3H2O. A solution of this salt is also pink and rapidly gives 3 mol AgCl on
titration with silver nitrate solution. When the pink solid is heated, it loses 1 mol H2O to give a purple solid with the
same ratio of NH3:Cl:Co. The purple solid releases two of its chloride ions rapidly; then on dissolution and titration
with AgNO3, releases one of its chloride ions slowly. Deduce the structures of the two octahedral complexes and draw
and name them.

Since the pink solid rapidly gives 3 equivalents of AgCl on titration with silver nitrate, the chloride ions must not be
covalently bound to the metal, and are likely counterions. This suggests that the water molecule is a covalently bound
ligand in this initial complex. On heating, the water is displaced by a chloro ligand, so that the formula for the new
compound is just CoCl35NH3. This complex has two ionic chloride, and one covalently bound chloro ligand. Equations
for these transformations are given below. These reactions are closely related to ones performed in the laboratory in
Experiments 1 and 2.

[Co(NH3)5(OH2)]Cl3 + 3 Ag+ [Co(NH3)5(OH2)]3+ + 3 AgCl

[Co(NH3)5(OH2)]3+ + Cl/heat [Co(NH3)5(Cl)]2+

[Co(NH3)5(Cl)]Cl2 + 3 Ag+ (fast) [Co(NH3)5(Cl)] + 2 AgCl (slow) [Co(NH3)5(OH2)]3+ + AgCl

Pentammineaquacobalt(III) Pentamminechlorocobalt(III)

13. The hydrated chromium chloride that is available commercially has the overall composition CrCl36H2O. On boiling
an aqueous solution of this salt, it becomes violet and has a molar electrical conductivity similar to that of
[Co(NH3)6]Cl3. In contrast, CrCl35H2O is green and has a lower molar conductivity in solution. If a dilute acidified
solution of the green complex is allowed to stand for several hours, it turns violet. Interpret these observations with
structural diagrams.

The hydrated chromium chloride sold as CrCl3.6H2O is actually trans-[Cr(OH2)4Cl2]Cl2H2O. On complete aquation it
is converted into [Cr(OH2)6]3+ (in neutral of weakly acidic solution). However, partial dehydration of the commercial
compound can produce CrCl35H2O, which is the partly-aquated complex [Cr(OH2)5Cl]Cl2. The conductivity of these
three species will be different. The hexahydrate forms a 1:1 electrolyte, the pentahydrate a 1:2 electrolyte, and the fully
aquated complex [Cr(OH2)6]Cl3 a 1:3 electrolyte. The different ligand field strengths of Cl and H2O lead to different
colours for the ions in both solution and in the solid state. Aquation also occurs more slowly at room temperature,
which explains why a solution left for several hours turns violet.

Pentaaquachlorochromium(III) Hexaaquachromium(III)

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14. The complex first denoted -[PtCl2(NH3)2] was identified as the trans-isomer. (The cis isomer was denoted .) It
reacts slowly with solid Ag2O to produce [Pt(NH3)2(OH2)2]2+. This complex does not react with ethylendiamine to give
a chelated complex. Name and draw the structure of the diaqua complex.

The fact that the aqua complex does not react with en suggests that it too must be the trans isomer, since this chelating
ligand cannot stretch across a metal to occupy two trans positions on any metal ion; indeed en complexes are always
cis. The complex is thus trans-diamminediaquaplatinum(II):

15. The third isomer (neither nor , see previous question) of composition PtCl22NH3 is an insoluble solid which,
when ground with AgNO3, gives a solution containing [Pt(NH3)4](NO3)2 and a new solid phase of composition
Ag2[PtCl4]. Give the structures and names of each of these Pt(II) compounds.

The overall formula is satisfied by the complex salt [Pt(NH3)4][PtCl4], and this fits the observed reaction:

[Pt(NH3)4][PtCl4] + 2 AgNO3 [Pt(NH3)4](NO3)2 + Ag2[PtCl4] (s)

16. Phosphine and arsine analogues of [PtCl2(NH3)2] were prepared in 1934 by Jensen. He reported zero dipole moments
for the isomers, where the designation represented the products of a synthetic route analogous to that of the
ammines. Give structures of both the and complexes with the two ligand types (PR3 and AsR3).

The trans isomers have D2h symmetry and hence do not have a dipole moment (no molecule belonging to a D group
can be polar. However, the cis isomers belong to the point group C2v, and hence are polar. Thus the -isomers must be
trans. Hence the isomers are cis. For the structures below I have used trimethylphosphine for simplicity, whereas
Jensen actually used the very similar triethylphosphine. The related arsine complexes have identical structures. The
reason that alkylphosphines and alkylarsines are used to mimic the chemistry of NH3 is that the more closely-related
PH3 and AsH3 are both highly toxic and highly reactive, inflaming spontaneously on exposure to air.
Triethylphosphine is somewhat more stable, does not burn spontaneously, and can be handled easily under a nitrogen
atomosphere. However, like all phosphines and arsines, these compounds stink terribly, and Jensens 1930s lab must
have been a dreadful place to be!

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17. Describe the differences in the 31P-NMR spectra of the cis and trans isomers of the phosphines in the previous
problem.

In both isomers, the two phosphorus atoms will be in identical chemical environments, so that they will in each case
give a single 31P signal. However, they will have a significantly different chemical shift. The direction of the shift is
crucially dependent on bond angles, and has no simple correlation with electronegativity effects as do 1H NMR spectra.
However, because platinum is 33% 195Pt (I = ), the spectra of both compounds will show typical satellite spectra.
The overall pattern looks like a 1:4:1 triplet. The spacing between the outer lines is 1J(31P-195Pt), and this value will
also be quite different for the cis and trans isomers.

typical 31P NMR spectrum for typical 31P NMR spectrum for
W-phosphine complexes where
Pt-phosphine complexes where phosphine(s) is(are) equivalent
phosphine(s) is(are) equivalent

31P 31P

18. (a) Indicate how NMR spectra might be used to distinguish the cis and trans isomers of [W(CO)4(PMe3)2]. Identify the
type of spectra you should run, and what you expect to see.

For similar reasons as discussed in #17 the two isomers should both show a singlet with small satellites due to the 14.4%
183
W isotope (I = ) (triplet in a 1:12:1 intensity ratio) (above). The size of 1J(31P-183W) and the chemical shifts of the
two signals would be different, but without knowing which spectrum went with which compound, it would not be possible
to tell them apart. However, it would be possible to distinguish the two isomers from 13C NMR spectra of the carbonyl
ligands in the two complexes. Remember that 13C is only about 1% abundant. Thus only one in 25 complexes will on
average have a single spin-active carbonyl group. However, that 13C nucleus would couple to the 100% abundant 31P
nuclei (I = ), and the signal is expected to be a triplet when the two P atoms are identical, as in the trans isomer, and a
doublet of doublets when the two P atoms are inequivalent, as in the cis isomer. Also the cis isomer is expected to display
two different signals; each signal will have the pattern shown in the figure at right, but the spacings (i.e. the 13C31P
coupling constants) are not expected to be the same. If good signal to noise can be achieved (not easy!), it may be possible
to see the weak tungsten satellites as well.

PPh3 expected 13C NMR PPh3 expected 13C NMR

spectrum for the PPh3 spectrum for the
OC CO trans isomer from two OC
W W cis isomer from two
OC CO equivalent P atoms, flanked OC CO inequivalent P atoms,
by 183W satelites flanked by 183W satelites
PPh3 CO

13C 13C

(b) What features of their NMR spectra would distinguish a complex [M(CO)3(PR3)2] of trigonal bipyramid geometry
with the phosphine ligands in the axial positions from one with the phosphine ligands in the equatorial plane?

Here again we need to use 13C NMR from a metal carbonyl. The trans isomer should display a single 1:2:1 triplet from
2
J(13C-31P). The cis isomer has inequivalent CO groups, so that two signals, both 1:2:1 triplets, are expected with different
chemical shift and different size of coupling constant to 31P.

expected 13C NMR CO expected 13C NMR

PPh3 spectrum for the PPh3 Cequatorial spectrum for the
CO Caxial
trans isomer from two OC M cis isomer from two
OC M equivalent P atoms both PPh3 quivalent P atoms on
CO axial CO equatorial sites
PPh3

13C 13C

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19. In trans-[W(CO)4(PR3)2], the alkylphosphine ligands define the z-axis of the coordinate system. Sketch the symmetry-
adapted linear combination of -orbitals from the two P atoms that can combine with the metal dz2 orbital. Show the
bonding and antibonding combinations that may be formed.

The in-phase combination of two -donor orbitals (A1g symmetry in D4h) from the two axial PH3 groups is shown at left,
with the metal dz2 orbital in the middle (A1g symmetry in D4h), that leads to a bonding combination (1A1g) in the complex
shown at the right. (Note that the colours switch between the two orbital plots from HyperChem; thus the bond MO
should be green-pink-green-pink-green.

+ M

The out-of-phase combination leads to an anti-bonding orbital (2A1g).

+ M

20. Determine the configuration (in the form t 2mg egn or e m t 2n , as appropriate), the number of unpaired electrons, and the
ligand field stabilization energy as a multiple of o or T for each of the following complexes using the
spectrochemical series to decide, where relevant, which are likely to be strong-field and which weak-field. (a)
[Co(NH3)6]3+; (b) [Fe(OH2)6]2+; (c) [Fe(CN)6]3; (d) [Cr(NH3)6]3+; (e) [W(CO)6]; (f) [FeCl4]2 and (g) [Ni(CO)4].

(a) [Co(NH3)6]3+ Since the NH3 ligands are neutral, this is a Co3+ complex, so we are dealing with a d6 metal ion.
Although ammonia is in the middle of the spectrochemical series, a metal in the 3+ oxidation state is past the middle of the
metal series, so the combination is very likely to be a low-spin configuration, t 26g eg0 . Indeed, octahedral d6 has S = 0 (no
unpaired electrons) and is diamagnetic. The LFSE is 6 0.4O = 2.4O. Note that this is the largest possible LFSE for an
octahedral complex.

(b) [Fe(OH2)6]2+ The iron ion in this octahedral complex with six neutral water ligands is in the 2+ oxidation state, and
water is low on the spectrochemical series. We certainly expect this d6 ion to be in a high spin configuration, t 24g eg2 , with
S = 2. That is, it has four unpaired electrons and is strongly paramagnetic. The LFSE is 4 0.4O 2 0.6O = 0.4O.
Note the much smaller LFSE compared to the low spin d6 case discussed in (a)!

(c) [Fe(CN)6]3 The iron in this octahedral complex with six 1 cyanide ligands is in the 3+ oxidation state, and cyanide
is high on the spectrochemical series. This is almost certainly a complex with a low spin configuration. Fe3+ is a d5 metal
ion, and hence the configuration will be t 25g eg0 , with S = . The LFSE is 5 0.4O 0 0.6O = 2.0O.

(d) [Cr(NH3)6]3+ The complex contains six neutral ammonia ligands, so it is Cr3+, which is a d3 metal ion. There is only
one electron configuration for octahedral d3, i.e. t 23g eg0 , which means that there are three unpaired electrons and S = 3/2.
The LFSE is 3 0.4O 0 0.6O = 1.2O

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(e) [W(CO)6] Carbon monoxide is neutral and is very high on the spectrochemical series. It is a strong field ligand. The
metal is therefore in the neutral oxidation state. However, in the complex we promote the 4s electrons into 3d, so that it is
nonetheless a d6 metal atom. We expect a low spin complex, with configuration t 26g eg0 , and S = 0. The LFSE is 2.4O.
(f) [FeCl4]2 This is a tetrahedral complex, because the ligands are 1, the metal is therefore 2+, and Fe2+ is d6, which is
not a candidate for square planar geometry. Remember that all tetrahedral complexes are high spin because T is
inherently small {T = (4/9) O}. Thus the expected electron configuration is e 3t 23 , and S = 2.0 for four unpaired
electrons, and strongly paramagnetic. The LFSE is 3 0.6T 3 0.4T = 0.6T.

(g) [Ni(CO)4] This is also a tetrahedral complex, because the ligands are neutral, the metal is (after promotion of the 4s
electrons) d10, and hence not a candidate for square planar geometry. Of course, regardless of geometry, complexes of d10
metal atoms and ions will always have LFSE = 0, and this complex is no exception.

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