12. Practice with Tanabe-Sugano diagrams. In Appendix 5 to Shriver-Atkins-Langford are Tanabe-Sugano diagrams.

Use these
diagrams to assign the spectra of the aqua ions given below. Where possible, esitmate the value of B. Use your results to
construct a “metal series” for O using the water ligand. Assume all are octahedral, but remember that a Jahn-Teller
distortion is possible, but not always observed, for all ions with a T1g or a T2g ground term.
13. The free gas-phase ion V3+ 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 V3+.

The diagram at right shows the relative energies of the 3 F, 1 D and 3 P terms. It can be seen that 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 .

14. 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(NH3 )6 ]3+, (b) [Ti(OH2 )6 ]3+, (c) high-spin [Fe(OH2 )6 ]3+.

(a) Low-spin [Rh(NH3 )6 ]3+ From the electron configuration for neutral Rh (5s2 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(OH2 )6 ]3+ From the electron configuration for neutral Ti (4s2 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 T2g (See question 1).

(c) High-spin [Fe(OH2 )6 ]3+ From the electron configuration for neutral Fe (4s2 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.

15. Using the Tanabe-Sugano diagrams in the appendices, estimate O and B for (a) [Ni(OH2 )6 ]2+ (absorptions at 8500, 15 400,
and 26 000 cm–1 ) and (b) ) [Ni(NH3 )6 ]2+ (absorptions at 10 700, 17 500, and 28 200 cm–1 ).

(a) [Ni(OH2 )6 ]2+ According to the d 8 T-S diagram, the

absorptions can be assigned as follows:
8500 cm–1 3
T2g 3 A 2g
–1 3
15 400 cm T1g 3 A 2g
–1 3
26 000 cm T1g 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 Ni2+ 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(NH3 )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 NH3
is higher in the nehpelauxetic series than is H2 O.

16. Explain why [FeF6 ]3– is colourless whereas [CoF6 ]3– is coloured,
but exhibits only a single band in the visible region of the
electronic spectrum.

Both are M3+, 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 (see
question 1), 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
Eg 5 T2g . This means the complex will have significant colour
even in relatively dilute solution.
17. The Racah parameter B is 460 cm–1 in [Co(CN)6 ]3– and 615 cm–1 in [Co(NH3 )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 NH3 can form molecular orbitals only with the metal eg
orbitals, while cyanide can form molecular orbitals with the metal eg and t2g orbitals. The formation of molecular orbitals is
the way that electrons are delocalized, and this is precisely what the nephelauxetic effect measures.

18. [Cr(OH2 )6 ]3+ ions are pale blue-green but chromate ion [CrO4 ]2– is an intense yellow. Characterize the origins of the
transitions and explain the relative intensities.

[Cr(OH2 )6 ]3+ ions have a d 3 configuration, while [CrO4 ]2– has a d 0 configuration. Thus in the Cr(II) 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.

19. Name the species and draw the structures of (a) Fe(CO)5 , (b) Ni(CO)4 , (c) Mo(CO)6 , (d) Mn2 (CO)10 , (e) V(CO)6 , (f)
[PtCl3 (C2 H4 )]– .

The names of the metal carbonyls first specify the number of CO ligands, then the number and type of metal atom(s), and
finally the oxidation state of the metal(s). The structures of the metal carbonyls generally have simple, symmetrical shapes
that correspond to the CO ligands taking up positions that place them as far apart from one another as possible.

(a) Fe(CO)5 pentacarbonyliron(0) Forms a regular trigonal bipyramid

(b) Ni(CO)4 tetracarbonylnickel(0) Regular tetrahedron
(c) Mo(CO)6 hexacarbonylmolybdenum(0) Regular octahedron
(d) Mn2 (CO)10 dodecacarbonyldimanganese(0) The two octahedral fragments are joined, and rotated to be staggered.
(e) V(CO)6 hexacarbonylvandaium(0) Regular octahedron
(f) [PtCl3 (C2 H4 )]– trichloro(ethene)platinate(II) This is named just like the classical coordination complexes we have
considered earlier in this course. It is “square planar”, and this mo de maximizes the “side-on” overlap between the metal d-
orbitals and the -acceptor orbitals on the ethylene. Because the ethylene group sticks up and down, the molecule itself is not
planar, but the geometry and bonding is that of a d 8 square planar group. Although the HyperChem model below does not
show this, it is possible to draw [PtCl3 (C2 H4 )]– in such a way that the ethylene ligand is attached at the midpoint of the C=C
bond. This is realistic, because that is where the filled -orbital that is the -donor orbital is centred. Indeed, such
complexes are known to rotate in solution, quite literally “spinning” on the axis defined by the Pt atom and the midpoint of
the C=C bond.

(a) (b) (c) (d) (e) (f)

20. Count the number of valence electrons in each of the complexes listed in question 19. Do any of them deviate from the 18-
electron rule? If so, is this reflected in their structure or chemical properties?

(a) Fe(CO)5 Fe has 8 valence electrons, and 5 CO contribute 10 electrons, for a total of 18.

(b) Ni(CO)4 Ni has 10 valence electrons, and 4 CO contribute 8 electrons, for a total of 18.

(c) Mo(CO)6 Mo has 6 valence electrons, and 6 CO contribute 12, for a total of 18.

(d) Mn2 (CO)10 Mn has 7 valence electrons, and 5 CO per Mn contribute 10 electrons, for a total of 17. An
additional electron is contributed by the Mn–Mn bond, for a total of 18. Another way to count this
dimeric compound is to calculate the whole cluster as follows: 2 Mn = 14 e– , 10 CO = 20 e– , one
Mn–Mn bond = 2 e– for a total of 36 e– for two metals. Therefore divide by 2 to get 18 e– per
metal atom.

(e) V(CO)6 V has 5 valence electrons, and 6 CO contribute 12, for a total of 17 electrons. This octahedral
complex is electron deficient. It can be made only because it is coordinatively saturated by the six
CO ligands which block rapid access to the V atom. However, it is much more reactive than its 18
e– analogues such as Cr(CO)6 . V(CO)6 is readily reduced to [V(CO)6 ]– , an 18 e– complex anion.
It is also very highly coloured, in sharp contrast to Cr(CO)6 and Ni(CO)4 which are colourless.

(f) [PtCl 3 (C2 H4 )]– Pt has 10 valence electrons, but is in the +2 oxidation state, so 8 electrons. The three chloride
ligands contribute 6 electrons, and the ethylene ligand also contributes 2 electrons. This makes for
a total of 16 electrons. This is the “correct” count for a d 8 square planar complex.

21. Using the 18-electron rule as a guide, indicate the probable number of carbonyl ligands in (a) [W(6 -C6 H6 )(CO)n ], (b)
[Rh(5 -C5 H5 )(CO)n ], and (c) [Ru 3 (CO)n ].

(a) [W(η 6 -C6 H6 )(CO)n] A W atom has 6 electrons, 6 benzene has 6 electrons, so to get 18 electrons needs 6 more,
therefore three CO ligands donating 2 electrons each are required. n = 3

(b) [Rh(η 5 -C5 H5 )(CO)n] A Rh atom has 9 electrons when neutral, Cp contributes 5, so we need 4 more electrons,
contributed by two CO. n = 2.

(c) [Ru3 (CO)n] This complex could be linear (i.e. Ru–Ru–Ru), with two Ru–Ru bonds, or triangular with three
Ru–Ru bonds. If it were linear, there would be no way to satisfy the 18-electron rule for the two
Ru atoms at the end, regardless of the value of n:

for all n, 18  8 + 1 (for Ru–Ru bond ) + 2n

Therefore this must be a triangular cluster, with two Ru–Ru bonds per Ru atom. Therefore each
Ru has 8 electrons, the M–M bonds contribute 4 electrons, and 6 extra electrons are required per
Ru atom. Thus Ru(CO)3  3 = Ru 3 (CO)12 .