1

Chemistry 3840 Answers to Assignment #2

Topic: Coordination chemistry.

1. Solutions of the complexes [Co(NH
3
)
6
]
2+
, [Co(OH
2
)
6
]
2+
and [CoCl
4
]
2
are coloured. One is pink, another is yellow,
and the third is blue. Considering the spectrochemical series and the relative magnitudes of
T
and
O
try to assign
each colour to one of the complexes.

[Co(NH
3
)
6
]
2+
, [Co(OH
2
)
6
]
2+
and [CoCl
4
]
2
. First we must establish the complement of the light that is absorbed, and for
this we need a colour wheel. Remember that a coloured solution of a metal complex absorbs the photons of white light
that are not transmitted, and it is the absorbed photons that we really need to understand.

Thus we see that the complement of pink (red) is cyan, the complement of yellow is blue and the complement of blue is
yellow. In terms of increasing photon energy, yellow < cyan < blue. We therefore can expect that the complexes with the
lowest will be blue, followed by the pink and lastly the yellow with the largest .

Now we consider the expected values. Obviously [CoCl
4
]
2
will have the smallest , since
T
<<
O
[therefore it is the
blue complex]. Then comes [Co(OH
2
)
6
]
2+
[therefore this is the pink complex] followed by [Co(NH
3
)
6
]
2+
[which is thus
the yellow complex], since for these two octahedral complexes, ammonia is higher on the spectrochemical series than is
water. Although these are reasonable assignments (and correct in this case), in general colour can be quite deceiving, and
a complex may have more than one band in different regions of the colour spectrum, and the blended colour can be quite
deceiving.

2. A neutral macrocyclic ligand with four donor atoms produces a red diamagnetic low-spin d
8
complex of Ni(II) if the
anion is the weakly coordinating perchlorate ion. When perchlorate is replaced by two thiocyanate ions SCN

, the
complex turns violet and is high-spin with two unpaired electrons. Interpret the change in terms of the structure.

The perchlorate ion either does not coordinate, or provides a sufficiently weak ligand field, that the complex with this
anion is effectively square planar. In square planar d
8
complexes (D
4h
symmetry), all 8 electrons are paired, and the
complex will be diamagnetic. However, when strong axial ligands are introduced, the electronic structure approximates
that of an octahedral complex, and octahedral d
8
is paramagnetic with two unpaired electrons.

octahedral limit
square planar limit
xz,yz
z
2
,x
2
-y
2
xz,yz,xy
xy
z
2
x
2
-y
2


3. Bearing in mind the Jahn-Teller theorem, predict the structure of [Cr(OH
2
)
6
]
2+
.

The main consequence of the so-called first-order Jahn-Teller theorem for our study is that a nonlinear molecule or ion
with an orbitally degenerate ground state is not as stable as a distorted version of the molecule or ion whenever the

2
distortion is capable of removing the degeneracy (i.e. by symmetry lowering). We expect [Cr(OH
2
)
6
]
2+
to be high spin d
4
,
and thus will have the configuration
1 3
2 g g
e t , which is orbitally degenerate in that the single electron can be either in the d
z
2

or the d
x
2
-y
2
orbital. Therefore by the Jahn-Teller theorem, the complex should not have full O
h
symmetry. A tetragonal
distortion whereby two trans metal-ligand bonds are elongated and the other four shortened removes the degeneracy, and
lowers the d
z
2
and raises the d
x
2
-y
2
orbital energy. The single electron will thus occupy the d
z
2
orbital.

This is the most common distortion observed for octahedral complexes of high-spin d
4
, low-spin d
7
, and d
9
metal ions, all
of which possess e
g
degeneracy and exhibit measurable Jahn-Teller distortions. Such distortions are generally quite mild,
with the exception of Cu(II), d
9
, which can often distort well towards a four coordinate geometry. This is why we
generally attribute only four water ligands to the inner coordination sphere of the Cu
2+
aqua ion, even though this is not a
tetrahedral complex. In fact, it is tetragonally distorted octahedral, with four close and two further away water ligands.

4. The spectrum of d
1
Ti
3+
(aq) is attributed to a single electronic transition e
g
t
2g
. The band shown in Fig. 10 in the
chapter is not symmetrical and suggests that more than one state is involved. Suggest how to explain this observation
using the Jahn-Teller theorem.

Generally distortions of the t
2g
level are less significant than from the e
g
level.
This may lead to the conclusion that d
1
Ti
3+
(aq) should not be distorted. However,
in the electronic spectrum we are measuring the transition e
g
t
2g
, which results
in a short-lived electronic exited state which has a
1 0
2 g g
e t configuration. This
suggests that distortion can occur in the excited state. Therefore the single
electronic transition is in reality the superposition of two transitions, one to the
symmetrical excited state, the other to a distorted excited state, and the result is an
asymmetric absorption peak in the electronic spectrum of the Ti
3+
aqua ion. The
spectrum shown at right is not quite realistic, and under-emphasizes the distorted
shape of the peak.

5. Construct a complete orbital energy diagram for a tetragonally-distorted 6-coordinate complex, in which the axial
bonds are weakened. You may thing of this as an extreme tetragonal octahedral complex in which the axial bonds are
weakened to the limit. Consider -bonding only. Include energy levels and sketch topologically correct orbitals.

I will leave this to you to do. We have developed this diagram in lecture in detail, and it is also in your notes. Here is
the result that you should obtain:










3
6. Practice with Tanabe-Sugano diagrams.
(a) Cr(OH
2
)
6
2+

Two bands are observed: 14,200 cm
-1
; >36000 cm
-1
Expect a high-spin configuration because the aqua ligand is a
weak-field ligand. Therefore, for a d
4
ion, we obtain a (t
2g
)
3

(e
g
)
1
configuration.
From the Tanabe-Sugano diagram, we see that the
5
E
g
is the
ground state. The only quintet excited state shown on the
Tanabe-Sugano diagram is
5
T
2g
, therefore, the second band
>36000 cm
-1
must be a charge-transfer (CT) band.
The
5
T
2g

5
E
g
excitation is the lowest (and the only) spin-allowed excitation (Laporte forbidden). The energy corresponds
directly to
O
.
Hence,
O
= 14,200 cm
-1
. The value of B cannot be determined.





(b) Ti(OH
2
)
3+



Free-ion configuration: d
1
electron configuration in an O
h
complex: (t
2g
)
1
Note that there are no Tanabe-Sugano diagrams for d
1
and d
9
. Both, these systems have one ground state (
2
T
2g
) and one
excited state (
2
E
g
) with the spin-allowed transition
2
E
g

2
T
2g
.
The
2
E
g
state is susceptible to Jahn-Teller distortion. Thus the higher energy band corresponds to
O
, the lower to the
distorted transition.
Hence,
O
= 21,000 cm
-1
. The value of B cannot be determined.
The second band >35,000 cm
-1
is a CT band, as in part (a).













4
(c) Fe(OH
2
)
6
2+


Free-ion configuration: d
6

Probably weak field, hence high spin: (t
2g
)
4
(e
g
)
2
.
From the Tanabe-Sugano diagram, we see that the ground
state is
5
T
2g
. Here again, only one quintet excited state is
available:
5
E
g
. The excited state is also susceptible to Jahn-
Teller distortion, as a consequence, there is a splitting of
the band. The higher transition corresponds to
O
.
Hence,
O
= 11,000 cm
-1
. The value of B cannot be
determined.







(d) V(OH
2
)
6
3+


Free-ion configuration: d
2

From the Tanabe-Sugano diagram, we see that is
3
T
1g
is the ground state. The first excited state is
3
T
2g
, the second is
3
T
1g
. Both bands are d-d
transitions.
For 17,000 cm
-1
:
3
T
2g

3
T
1g

25,000 cm
-1
:
3
T
1g
(P)
3
T
1g
(F)
Ratio of 25,000/17,000 = 1.5. This ratio can be
founding the Tanabe-Sugano diagram as indicated.
The horizontal intercept for the first transition gives
E/B = 23
therefore, B = 17,000 cm
-1
/23 = 740 cm
-1

O
/B = 25, hence,
O
= 25 740 cm
-1
= 18,500 cm
-1
.
These transitions are spin-allowed and Laporte forbidden.




5
(e) Mn(OH
2
)
6
2+


Free-ion configuration: d
5
(high spin)
From the Tanabe-Sugano diagram, we see that is
6
A
1g

is the ground state. There are no sextet excited states,
so all transitions are spin-forbidden.
1. 18,000 cm
-1
:
4
T
1g

6
A
1g

2. 23,000 cm
-1
:
4
T
2g

6
A
1g
3. 24,500 cm
-1
:
2
T
2g

6
A
1g

4. 24,700 cm
-1
:
4
A
1g
,
4
E
g

6
A
1g

5. 28,300 cm
-1
:
2
A
2g
,
2
T
1g

6
A
1g

6. 30,000 cm
-1
:
4
E
g

6
A
1g


Ratio of 2:1 1.28:1
3:1 1.36:1
4:1 1.37:1
5:1 1.57:1
6:1 1.67:1
These ratios fit at the vertical intercept of
O
/B = 11.
For the lowest transition: E/B =24, B = 18,000 cm
-1
/24 = 750 cm
-1
.
Since
O
/B = 11,
O
= 9000 cm
-1
. (textbook has
O
= 8500 cm
-1
)



7. The free gas-phase ion V
3+
has a
3
F ground term. The
1
D and
3
P terms lie respectively 10 642 cm
1
and 12 920 cm
1

above it. The energies of the terms are given in terms of Racah parameters as E(
3
F) = A 8B, E(
3
P) = A + 7B, E(
1
D) = A
3B + 2C. Calculate the values of B and C for V
3+
.

The 10 642 cm
1
energy gap between the
3
F and
1
D terms is 5B + 2C, while the 12 920 cm
1
energy gap between the
3
F and
3
P terms is 15B. From the two equations:
5B + 2C = 10 642 cm
1

15B = 12 920 cm
1

you can determine that B = 12 920 cm
1
/ 15 = 861 cm
1
and C = 3170 cm
1
. C/B = 3.68

8. Write the d orbital configurations and then use the Tanabe-Sugano diagrams in the appendices to identify the ground
electronic term of (a) low-spin [Rh(NH
3
)
6
]
3+
, (b) [Ti(OH
2
)
6
]
3+
, (c) high-spin [Fe(OH
2
)
6
]
3+
.

(a) Low-spin [Rh(NH
3
)
6
]
3+
From the electron configuration for neutral Rh (5s
2
4d
7
) we get 9 electrons; 3+ reduces that to
6, so it is a d
6
ion. From the T-S we read off the ground state from the bottom line to the right of the vertical divider for
high and low spin. So for this ion it is
1
A
1g
. We supply the g because it is an octahedral complex.

(b) [Ti(OH
2
)
6
]
3+
From the electron configuration for neutral Ti (4s
2
3d
2
) we get 4 electrons, remove 3 give d
1
. There is no
low/high spin distinction. There is no T-S diagram. But we know that the ground state for d
1
is always
2
T
2g
, since that one
electron occupies a t
2g
orbital.

(c) High-spin [Fe(OH
2
)
6
]
3+
From the electron configuration for neutral Fe (4s
2
3d
6
) we get 8 electrons, so as 3+ it is a d
5

ion in high spin form. The T-S diagram to the left of the vertical dividing line then indicates it to have an
6
A
1g
ground
state.





6

9. Using the Tanabe-Sugano diagrams in the appendices, estimate
O
and B for (a) [Ni(OH
2
)
6
]
2+
(absorptions at 8500, 15
400, and 26 000 cm
1
) and (b) [Ni(NH
3
)
6
]
2+
(absorptions at 10 700, 17 500, and 28 200 cm
1
).

(a) [Ni(OH
2
)
6
]
2+
According to the d
8
T-S diagram, the
absorptions can be assigned as follows:
8500 cm
1

3
T
2g

3
A
2g

15 400 cm
1

3
T
1g

3
A
2g

26 000 cm
1

3
T
1g

3
A
2g

The ratios 13,800/8,500 = 1.6 and 25,300/8500 = 3.0 can be used
to estimate
O
/B 11. Using this value we calculate
O
= 8,500
cm
1
and B 770 cm
1
. Note that B for a gas-phase Ni
2+
ion is
1080 cm
1
. The fact that B for the complex is only ~70% of the
free ion value is an example of the nephelauxetic effect.

(b) [Ni(NH
3
)
6
]
2+
The absorptions for this complex are 10 700, 17
500, and 28 200 cm
1
with the same assignment as in (a). The
ratios are 1.6 and 2.6, leading to
O
/B 15. Thus calculate
O
=
10,750 cm
1
and B 720 cm
1
. It is sensible that B for the
ammine complex is lower than for the aqua complex, since NH
3

is higher in the nehpelauxetic series than is H
2
O.

10. Explain why [FeF
6
]
3
is colourless whereas [CoF
6
]
3
is coloured,
but exhibits only a single band in the visible region of the
electronic spectrum.

Both are M
3+
, so the iron is d
5
, while the cobalt is d
6
. With F

as
the ligand, very weak field, we expect the complexes to both be
high spin. In high spin d
5
, to the left of the dividing line, the
ground state is
6
A
1g
, and there are no sextet excited states. All
transitions are therefore spin-forbidden, and the complexes will
be extremely pale, and it is not surprising that they appear
colourless in dilute solution. However, d
6
from the T-S diagram
is capable of a single spin-allowed d-d transition,
5
E
g

5
T
2g
. This
means the complex will have significant colour even in relatively
dilute solution.

11. The Racah parameter B is 460 cm
1
in [Co(CN)
6
]
3
and 615 cm
1
in [Co(NH
3
)
6
]
3+
. Consider the nature of the bonding
with the two ligands and explain the difference in nephelauxetic effect.

These two ligands are quite different with respect to the types of bonds they form with metal ions. Ammonia and cyanide
are both -bases, but cyanide is also a -acid. This difference means that NH
3
can form molecular orbitals only with the
metal e
g
orbitals, while cyanide can form molecular orbitals with the metal e
g
and t
2g
orbitals. The formation of molecular
orbitals is the way that electrons are delocalized, and this is precisely what the nephelauxetic effect measures.

12. [Cr(OH
2
)
6
]
3+
ions are pale blue-green but chromate ion [CrO
4
]
2
is an intense yellow. Characterize the origins of the
transitions and explain the relative intensities.

[Cr(OH
2
)
6
]
3+
ions have a d
3
configuration, while [CrO
4
]
2
has a d
0
configuration. Thus, in the Cr(III) aqua ion, there is the
possibility of spin-allowed, but Laporte-forbidden d-d bands in the electronic spectrum. However, such transitions are not
possible for the Cr(VI) chromate species. The colour of this ion must be due to LMCT bands (e.g. from the lone pair
oribitals on oxygen into the empty metal d orbitals. Such transitions are fully allowed, and this accounts for the intense
colour of the chromate ion.