Department of Chemistry

IIT Madras, Chennai 600036

Prof. Bhyrappa Jan-May 2022
B. Tech. Course: CY1001
Tutorial 1
Transition metal chemistry
1. Fill in the answers

(a) The o for (i) [Co(NH3)6]3+, (ii) [Ir(NH3)6]3+ and (iii) [Rh(NH3)6]3+ ions, increases
in the order: __(i) < (iii) < (ii)________________.

(b) The halide, I– is considered as __weak___ field ligand among halides (X– = F–, Cl–, Br– and
I–) in the spectrochemical series.

(c) The _two_fold degeneracy of the d-orbitals is the lowest energy for the copper centre in
[Cu(CN)4]3–.

(d) The spectrochemical series of metal ions, (a) Ni(II), (b) Co(III), and (c) Fe(III) in their
octahedral crystal field splitting follows the order: ____(b) > (c) > (a)_________.

(e) Among (i) [CoCl4]2–, (ii) [FeCl4]– and (iii) [NiCl4]2– ions, the complex ion with the highest
spin-only magnetic moment is _____(ii)________.

(f) The o for the ions (a) [CoF6]3–, (b) [Co(en)3]3+ and (c) [Co(ox)3]3–, follows the order:
____(a) < (c) < (b)________________.

(g) The molar absorptivity coefficients of the visible electronic absorption bands of
(i) [CrO4]2–, (ii) [Cr(OH2)6]2+ and (iii) [Mn(OH2)6]2+, follows the order: _____
_____(iii) < (ii) < (i)_____.

(h) The intensity of the d-d transitions of [CoCl4]2– is __higher__ than that of [CoCl6]4–.

2. Match the complex ions to their crystal field splitting parameter, o (nm).
Complex ion o, nm
1 [Cr(NH3)6]3+ V 575
2 [Cr(CN)6]3– X 671
3 [Cr(H2O)6]3+ Y 463
4 [CrF6]3– Z 376

Answer: 1-Y; 2-Z; 3-V; 4-X

3. Draw the d-orbital splitting (including orbital labels), their electron occupancy, CFSE
(including mean spin-pairing energy per electron pair, P) and spin-only magnetic moment
(in B.M.) of the complex ions, (a) [Fe(OH2)6]2+ and (b) [Mn(H2O)6]3+.

(a) t2g4 [dxy2 dxz1 dyz1], eg2 (dx2-y2 (1), dz2 (1)) ; CFSE: 0.4o so = 4.9 B.M.

(b) t2g3 (dxy1 dxz1 dyz1) eg1 (dx2-y2 (1), dz2 (0)) CFSE: 0.6o; so = 4.9 B.M.
4. Write the d-electron occupancy, CFSE (including mean spin-pairing energy per electron
pair, P), and indicate the strong Jahn-Teller distortion of the complex ions as in the table
below.

Complex ion d-electron occupancy Strong Jahn-Teller

dxy dz2 dyz dzx dx2–y2 CFSE Distortion (Yes/No)

[Co(NH3)6]3+ 2 0 2 2 0 2.4o - 2P No
[Cr(OH2)6]2+ 1 1 1 1 0 0.6o Yes
[MnCl6]4– 1 1 1 1 1 0 No

5. Draw the d-orbital splitting (including orbital labels), their electron occupancy, and spin-
only magnetic moment of the metal centres in the complex ions, (i) [Cu(CN)4]3– and (ii)
[Ni(CN)4]2–.

[Cu(CN)4]3– [Ni(CN)4]2–

(i) so = 0 (ii) so = 0

6. Calculate the CFSE (in cm–1) (exclude mean spin pairing energy per electron pair, P).
and spin-only magnetic moment (in B.M.) of the [Co(NH3)6]2+ ion shows the lowest
energy absorption band at 10,200 cm–1. (Inclusive of mean pairing energy per electron
pair).

d7 (high-spin): CFSE = 5x0. – 2x0.6 = 0.8o = 0.8 x 10,200 cm–1 = 8160 cm–1
so = 3.87 B.M.

7. The crystal structure of [Cr(OH2)6]2+ ion shows distorted octahedral geometry with 2 (Cr–
O) bonds longer and other 4 (Cr–O) bonds shorter. Name the type of distortion and draw the
d-orbital splitting (including orbital labels) and their electron occupancy of the chromium
centre.
 dx2-y2

eg
dz2
Doct
dxy

t2g

dyz dxz
Cr(II) - d4 (high-spin)
Oh Tetragonal distortion

8. For the ions (a) [CoCl4]2– and (b) [Fe(OH2)6]3+, indicate the ion that shows the highest
molar absorptivity coefficient value for their electronic absorption bands in the visible/NIR
region of the electromagnetic spectrum. Justify your answer.

(a) >> (b)

(a) - Td geometry. It lacks centre of symmetry and exhibits both Laporte and spin-allowed d-d
transitions.
(b) - Oh geometry. It has the centre of symmetry and shows both Laporte and spin-forbidden
d-d electronic transitions.

9. Assign (a) [MnF6]2– , (b) [TcF6]2– and (c) [ReF6]2– ions to their corresponding o values (i)
489, (ii) 352, and (iii) 305 nm and explain the trend.

(c) = 305 nm; (b) = 352 nm; (a) = 489 nm

Down the group, the size of d-orbitals (3d → 4d → 5d) increases, which induces greater
electron-electron repulsion between the metal ion and the fluoride ion, leading to larger 
values.

10. Calculate CFSE (in cm–1) including the pairing energy ‘P’ for the ion, [Mn(CN)6]4–.
(Given: o = 30,000 cm–1 and mean spin pairing energy per electron pair, P=24,000 cm–1).

CFSE = 2o – 2P = 2 x 30,000 cm–1 – 2 x 24,000 cm–1 = 12,000 cm–1