CHE3701/201/0/2023

Tutorial Letter 201/0/2023

Inorganic Chemistry III

CHE3701

Solutions to Assignment 01

Department of Chemistry

This tutorial letter contains important information

about your module.
QUESTION 1

a) Define the following terms. Illustrate your answer with a suitable diagram.

(i) HSAB (Hard Soft Acid Base) principle:

Hard acid: A Lewis acid with an acceptor centre of low polarizability, high
positive charge, small size. Soft Acids: A Lewis acid with an acceptor
centre of high polarizability, low positive charge, large size.
Hard Bases: A Lewis base with a donor centre of low polarizability, high
electron negativity, small size, no low energy empty d-orbitals. Soft base:
A Lewis base with a donor centre of high polarizability, low electron
negativity, large size, low energy empty d orbitals

HSAB principle: Hard (Lewis) acids prefer to bind to hard (Lewis) bases
Soft (Lewis) acids prefer to bind to soft (Lewis) bases.

(ii) Polydentate ligand: A ligand with more than one donor atom. A
polydentate ligand coordinates to a metal centre via two or more atoms,
forming two or more M−L bonds, giving a chelate complex.

Ethylenediamine (en)

(iii) Chelate effect: the thermodynamic stability of a chelate complex with

polydentate ligands is greater than that of a complex containing a

corresponding number of monodentate ligands.

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(iv) Bite angle: the X−M−Y angle where X and Y are the two donor atoms

of a chelating ligand.

(v) Denticity: the number of donor atoms through which a ligand coordinates to a

metal ion is defined as the denticity of the ligand.

b) (i) [Co(ONO)4(H2O)2]2-

diaquatetra(nitrito-O)cobaltate(II)

(ii) [Fe(en)2Cl2][BF4]

dichloridobis(ethylenediamine)iron(III) tetrafluoroborate

(iii) [Ni(NH3)4(ONO)2]·H2O

tetraamminedi(nitrito-O)nickel(II) hydrate

c) (i)

(ii)

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 (iii)

QUESTION 2

This module is limited to the study of metal complexes which exhibit strong Jahn-Teller
distortion

(i) [Ti(NH3)6]3+ Ti(III) has a d1 configuration

No Jahn-Teller distortion

(ii) [Cr(NH3)6]2+ Cr(II) has a d4 configuration

NH3 is a strong field ligand
Complex is low-spin

No Jahn-Teller distortion

(iii) [Cu(H2O)6]2+ Cu(II) has a d9 configuration

Strong
Jahn-Teller distortion

(iv) [Ni(NH3)6]2+ Ni(II) has a d8 configuration

No Jahn-Teller distortion

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In this module only d4 high-spin; d7 low-spin and d9 octahedral configurations are studied.

These configurations show strong Jahn-Teller distortion

QUESTION 3

(a)

There are no geometric isomers for tetrahedral [MA2B2] complexes

The SCN- ligand is ambidentate (thiocyanate and isothiocyanate), so linkage isomers are
possible

(b) There are 2 geometric isomers

trans-isomer cis-isomer

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(c)

-isomer -isomer

QUESTION 4

(a) [Ni(SCN)2(H2O)2]
(i) Ni(II) is d8

Coordination number = 4

(iii)

(iv) CFSE = – (0.6x – 0.4y) T

CFSE = – [0.6(4) – 0.4(4)] T
CFSE = – 0.8 T

(b) [Mn(acac)2Br2]2-
(i) Mn(II) is d5
acac and Br are weak field ligands, so the complex is high-spin

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(ii) Coordination number = 6

(iii)

(iv) CFSE = – (0.4x – 0.6y) o

CFSE = – [0.4(3) – 0.6(2)] o
CFSE = 0.0 o

(c) [Fe(bipy)3]2+
(i) Fe(II) is d6
bipy is a strong field ligand, so the complex is low-spin

(ii) Coordination number = 6

(iii)

(iv) CFSE = – (0.4x – 0.6y) o

CFSE = – [0.4(6) – 0.6(0)] o
CFSE = – 2.4 o + 2P

QUESTION 5

a) max = 500 nm

b) Electrons transitions between orbitals are show below:

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 The absorption of UV or visible radiation corresponds to the excitation of outer
(valence) electrons. There are two types of transitions which can be considered in this
module:
(i) Transitions involving σ, π and n electrons
(ii) Transitions involving charge-transfer electrons
A detailed explanation available in the study-guide and prescribed text-book.

c) [Co(H2O)6]3+ has Co(III) in d6 high-spin configuration.

H2O is a weak-field ligand which gives small o
[Co(CN)6]3+ has Co(III) in d6 low-spin configuration
CN- is a strong-field ligand which gives a large o

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A low max gives a high energy transition.

Therefore, large o and the spectrum corresponds to [Co(CN)6]3+

d) The broad band is due to the superposition of rotational and vibrational transitions on
the electronic transitions which gives rise to a combination of overlapping lines. This
then appears as a continuous absorption band.
e) A UV-Vis spectrophotometer records absorption spectra in the 200–800 nm range.
The light source consists of a deuterium lamp and a tungsten or halogen lamp.
The sample is in a solution in a quartz cuvette, usually with a 1 cm path length.
The pathlength is the distance the radiation travels through the cuvette.
The detector monitors the radiation transmitted through the sample.