CML101: Introduction to Chemistry

Inorganic Chemistry: Tutorial 1

There are few recap slides and after that you will find the questions
A common mistake students do while arriving the number of d electrons

Atomic number 26; Fe0 = [Ar] 3d64s2

Fe2+ = [Ar]3d6 (s-orbital electrons get oxidized first then d orbital
electrons get oxidize)
Fe3+ = [Ar] 3d5
 Splitting of the d-orbitals in an octahedral field
d - orbitals splitting in an
octahedral crystal field
eg

d - orbitals in a d x2 – y2 d z2
spherical field of
six ligands +0.6o
o or
10Dq
Energy

d - orbitals
stabilized by -0.4o
metal- ligand
electrostatic
attraction d xy d yz d xz

t2g

t2g : triply degenerate set of orbitals :

Eg: doubly degenerate set of orbitals
G = gerade: symmetric with respect to the centre of inversion
U = ungerade: antisymmetric w. r. t the centre of inversion
Barycenter: A point between objects where they balance each other
Splitting of the d-orbitals in an octahedral and Sq planer field

dx2‒y2

𝟒 𝟏
Δt = ΔO ≈ ΔO eg
𝟗 𝟐
Δsp
t2
dxy
ΔO
Δt

e dz2
t2g

Tetrahedral dxz, dyz

Octahedral
field Free ion field Square planar
field
The d5 and d6 low spin cases and the correct way to determine pairing energy contribution

+0.6o +0.6o

-0.4o -0.4o

CFSE = -2.0o +2P CFSE = -2.4o +2P

CFSE = -2.4o +3P

Always compare the extent of pairing with the situation before the splitting of five d orbitals occurred
 Colors and complementary colors of transition metal complexes

Complementary color is the color generated from the

left over wavelengths of light after certain wavelengths
are absorbed by the compound under study.

Yellow-------Violet
Green--------Purple
Blue green----Red
Blue------orange
Yellow green----purple violet

VIBGYOR
The Spectrochemical series
I  < Br  < S2- < SCN  < Cl  < F  < OH  < Ox < ONO  < H2O Weak field
< NCS < edta 4  < NH3  Py < en < bipy < Phen < NO2  < PPh3 < CN-  CO Strong field
Color depends on the splitting energy whereas intensity depends on the allowed transitions governed
by selection rules
 1. Laporte Selection Rule
Statement : Only allowed transitions are those occurring with a change in parity
(flip in the sign of one spatial coordinate.) OR During an electronic transition the
azimuthal quantum number can change only by  1 ( l = 1)
Practical meaning of the Laporte rule
Allowed transitions are those which occur between
gerade to ungerade or ungerade to gerade orbitals
Otto Laporte
German American
Allowed Physicist
gu & ug
Gerade = symmetric w r t centre of inversion
Not allowed (FORBIDDEN) Ungerade = antisymmetric w r t centre of inversion
g g & u u

This rule affects Octahedral and Square planar

complexes as they have center of symmetry

Tetrahedral complexes do not have center of

symmetry: therefore this rule does not apply

t2g eg is forbidden or according to Laporte selection rule d d transitions are not allowed !
 2. Spin Selection Rule

Statement : This rule states that transitions that involve a change in spin multiplicity are
forbidden. According to this rule, any transition for which  S = 0 is allowed and  S  0
is forbidden
Practical significance of the Spin Selection rule
During an electronic transition, the electron should not change its spin

d5 High spin (e.g [Mn(H2O)6]2+

eg eg

h

[GS] [ES] [GS] [ES] t2g t2g

S = 0 S  0 S  0 Forbidden
Allowed Forbidden
 d-Electron configurations which show Jahn Teller distortions

NO electronic degeneracy: Significant Jahn Teller

Normal Jahn Teller Distortion
NO Jahn Teller Distortion Distortion
Degeneracy in t2g
Degeneracy in eg

Spinels: In a normal spinel AIIBIIIO4 the tetrahedral sites are occupied by the A ions and the
octahedral sites by BIII ions: (AII)tet(BIII)2octO4. In an inverse spinals, the distribution is
(BIII)tet(AIIBIII)octO4.
1. Write down the d-orbital splitting diagram for [NiCl4]2− and [Ni(CN)4]2−. Will these complexes
be paramagnetic or diamagnetic?

2. 0 values of [Ru(H2O)6]2+ and [RuCl6]3- are nearly same but according to spectrochemical
series, the value for 0 for the chlorine should be less compared to H2O complex.
3. Calculate the CFSE values for [NiCl4]2−, [Mn(H2O)6]2+, [Co(NCS)6]4− and [Fe(CN)6]4−.
Explain why the CFSE for a low-spin d6 configuration contains a 2P term?
4. Calculate CFSE for [CoCl4]2- and [Fe(CN)6]3- (previous year question)
5. Sketch the ionic radii curve for the first series of transition metal ions in M2+ oxidation
state. Consider an octahedral geometry and cyanides as ligand. What will be the lowest
point if the metal has +3 oxidation state?
6. An octahedral cobalt(II) complex ion was found to have a magnetic moment of
1.92 𝜇B. What is the electronic configuration of the metal ion?

7. At room temperature, the observed value of 𝜇eff for [Cr(CH3OCH2CH2OCH3)3]Br2 is

4.75 𝜇B. Is the complex high-spin or low spin?
(8) The magnetic moment of [CoL6]SO4 is 3.8 BM. Choose correct ligands from water,
cyanide, chloride and ammonia, and draw the crystal-field splitting diagram.
(previous year questions)
9. Solutions of [Cr(OH2)6]3– ions are pale blue green but the chromate ion, CrO42–, is an intense
yellow. Characterize the origins of the transitions and explain the relative intensities.

10. An aqueous solution of Co(III) sulphate is diamagnetic but becomes paramagnetic when a
large excess of fluoride is added. Explain.
11. Given that [Co(OH2)6]3+ is low-spin, explain why it is possible to predict that [Co(bpy)3]3+ is
also low-spin.

12. The magnetic moment of the complex [Mn(NCS)6]4‒ is 6.06 𝜇B. What is its electron
configuration?