F LIMPOPO

UN YO
I VERSIT

Faculty of Science and Agriculture

SCHOOL OF PHYSICAL & MINERAL SCIENCES

Department of Chemistry

MODULE OUTLINE
(SCHB031)

2023

Compiled by: Prof MP Mokhonoana/Mr C Maswanganyi

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 MODULE OUTLINE
Inorganic Chemistry 3
Module Title
SCHB031 16
Module Code No. of
Credits
Chemistry SPMS
Department School
Pre-requisites SCHB021 Co-
Module Code requisites
Module
Code
Prof. M. P. Mokhonoana/ Mr. C. Maswanganyi
Module Lecturers
N-Block 2005B/N-Block 1017
Office Address
Malose.Mokhonoana@ul.ac.za 2336
Email Collet.Maswanganyi@ul.ac.za Telephone 2863
No.
09:00 – 12:30 am 24
Consultation Lecture
Time Periods
Test 1: 12/04/2023 10
Important Dates Test 2: 02/05/2023 Learning
Hours
2/1
Quarter/Semester
No. of Lectures: 28
Module Structure No. of Practical Sessions: 05
Assessment Description Weighting
Method

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Formative THEORY (60%): [Tests (60%) or 90% 60%
Tests and 10% Assignments and/or
Tutorials], Practicals (40 %),

Summative 1 × 3 h Written Examination 40%

MODULE DESCRIPTION
This module provides an introduction to modern concepts of inorganic
chemistry. The extraordinarily diverse chemistry of the elements is
organized in terms of molecular structure (& bonding), electronic
structures/properties, chemical reactivity and properties of inorganic
complexes and compounds. Selected topics in coordination chemistry,
organometallic chemistry, reactions, synthesis, and catalysis.

MODULE OBJECTIVES
(i) Build upon the concepts introduced in 1st and 2nd year Inorganic
Chemistry, and explore the varied aspects of transition metal chemistry

(ii) To teach students experimental methods and fundamental concepts in

coordination chemistry, organometallic chemistry, and inorganic materials
chemistry]

(iii) To provide a deeper understanding of bonding in transition metal

complexes based on valence bond, crystal field and simple molecular orbital
theories

(iv) To introduce the classification of ligands by electronic properties, as σ-

donors, π-donors, and π-acceptors

(v) To develop both the theoretical and descriptive aspects of inorganic

chemistry in order to provide a sound foundation for the SCHB081 and
higher courses

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(vi) To provide (via the laboratory course) in-depth training and experience
in practical aspects of inorganic chemistry, including synthesis, Conductivity,
UV/Vis, IR and NMR spectroscopies

(vii) To emphasize the synergy between the theoretical and practical aspects
of inorganic chemistry via close relationship of the laboratory work to the
other components of the course

MODULE CONTENT
1: Coordination Chemistry

1.1 Features of coordination compounds

(a) Metal Characteristics

(i) Electronic effects: Variable oxidation state and valence shell electron count

(ii) Coordination number

(b) Ligand characteristics

(i) Electronic effects: Purely σ-donor and π-acceptor and π-donor ligands. The
18-electron rule

(ii) Steric effects: Tolman’s cone angle (θ); dissociation constants and cone
angle values for phosphine complexes of nickel; Solid angle (Ω)

(c) π-acid ligands: General features, effects on the complex; Nature of the
interactions; Structural effects on the ligand; Evidence for synergic bonding;
Spectroscopic (IR) effects on the ligand.

1.2 Bonding Models in Transition Metal Complexes

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The following bonding theories are covered in this module to provide the student
with a clear understanding of the chemical behaviour and properties of transition
metal complexes, including reactivity, colour, and magnetism.

(a) Valence Bond Theory (VBT)

Hybrid orbitals and geometry of transition metal complexes, Outer orbital (ionic)
complexes and inner orbital (covalent) complexes, Magnetic properties of metal
complexes: paramagnetism v/s diamagnetism, Strengths and weaknesses of the
VBT, Pauling’s Electroneutrality Principle.

(b) Crystal Field Theory (CFT)

(i) Octahedral complexes: d-Orbital splitting in the presence of a ligand field; Crystal
Field Splitting Parameter (∆O) v/s Crystal-Field Stabilization Energy (CFSE);
Factors affecting the magnitude of ∆O; The Jorgensen parameters (ƒ & g);
Consequences of the CFT: strong-field/weak-field ligands & high-spin/low-spin
complexes and the spectrochemical series (a limitation of the CFT).

(ii) Tetrahedral and Square planar complexes; d-Orbital splitting patterns and
relationship to octahedral complexes; magnitudes of d-orbital splitting; Tetragonal
distortions (Jahn-Teller theorem); Consequences of the Jahn-Teller distortions;
Colour & Magnetic properties of complexes. Spinel structures: Normal spinels
versus inverse spinels (CFT approach to structure rationalization).

(c) Molecular orbital Theory (MOT)

(i) Ligand Field Theoretical (LFT) approach to covalent interactions; Molecular

energy level diagrams of different geometries. Ligand group orbitals (LGOs) and
their symmetry labels (Mulliken symbols).

(ii) Molecular orbital treatment of octahedral complexes

•σ- bonding and π-bonding in octahedral complexes
•Consequences of π-donation and π-acceptance (cf. spectrochemical series).

2: Organometallic Chemistry

2.1 General Introduction

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The 18 electron rule, electron counting and oxidation states, Metal-carbon (M─C)
bonds; Nomenclature, organometallic ligands, organometallic nucleophiles, linear
and cyclic π-electron systems, carbenes, d-block metal-carbonyls, spectroscopic
properties of carbonyl compounds, metallocenes, the Isolobal analogy describing
parallels between Organic and Inorganic Chemistry.

2.2 Classification of Reactions in Organometallic Chemistry

(i) Ligand Association (Addition), (ii) Ligand Dissociation, (iii) Migratory insertion,
(iv) Migratory elimination/β-hydride elimination, (v) Oxidative Addition
(requirements for, and mechanisms of), (vi) Reductive elimination (vii) Ligand
substitution

3: CATALYSIS (Homogeneous Catalysis)

General principles and Terminology used to describe the rate of a catalytic

reaction and its mechanism
(i) Free energy profiles for a reaction: catalyzed versus non-catalyzed, (ii) catalytic
cycles, (iii) catalytic turnover frequency, (iv) selective catalyst

•Homogeneous Catalyst Systems in Operation

Hydrogenation of alkenes (Wilkinson’s catalyst); Isomerization of olefins;

Hydroformylation (Oxo-process) of alkenes; Oxidation of alkenes (the Wacker
process) [Metal carbonyl-based catalyst systems]; BP-Monsanto Acetic Acid
Synthesis (Carbonylation of methanol)

4: The f-Block Elements (Lanthanides & Actinides)

Discovery and Occurrence, General & Periodic Characteristics, Electron

Configurations, Extraction and Separation of Lanthanides, Lanthanide contraction,
Coordination Chemistry of Lanthanides, Optical properties (UV-Vis spectra) and
NMR-shifting by Lanthanide Complexes, Applications of Lanthanide Elements.
Actinides.

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5: Platinum group metals
(Special topic; Used to be extensively treated in collaboration with Anglo Platinum;
Now only treated if time allows)

Terrestrial abundance and distribution, Introduction to refining methods, uses of the

elements and industrial demands, some properties of the elements, nickel,
palladium, platinum and copper, chemical reactivity and trends.

LEARNING OUTCOMES
Upon successful completion of this module, students should be able to:

(i) Identify and exploit the consequences of variable oxidation states in

transition metals

(ii) Describe metal-ligand bonds in terms of the valence bond theory, crystal
field theory, and molecular orbital theory.

(iii) Describe different types of mechanisms at work in inorganic reactions

(iv) Describe the chemistry of f-block elements (lanthanides and actinides)

(v) Use the isolobal analogy to bridge the gap between Organic and
Inorganic Chemistry

(vi) Be familiar with the concepts of Organometallic Chemistry (with

applications to homogeneous catalysis)

(vii) Generally understand and be able to apply concepts involving the

structure, bonding, electronic properties, and chemical reactivity of
coordination complexes, organometallic complexes, and inorganic materials

ASSESSMENT CRITERIA

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The student be able to explain and demonstrate the main features of
coordination chemistry, including but not limited to:

•Variable oxidation states and their implications on electronic structures,

reactivity and magnetic susceptibility.

•Nomenclature of coordination compounds, with emphasis on bridged

complexes.

•Isomerism in transition metal complexes

•How bonding theories allow interpretation of transition metal complexes.

This should be extended to f-block elements.

•Why organometallic compounds are central to industrial production, and

therefore underpin the economy.

REFERENCE MATERIALS FOR THE MODULE

PRESCRIBED BOOK

P. Atkins, T. Overton, J. Rourke, M. Weller and F. Armstrong, Shriver

& Atkins’ Inorganic Chemistry, 5th edition 2010.

OTHER RECOMMENDED TEXTBOOKS

G. L. Miessler and D. A. Tarr, Inorganic Chemistry, 3rd edition 2004.

Glen E. Rodgers, Descriptive Inorganic, coordination and solid-state

Chemistry, 3rd edition, Brooks/Cole, Cengage Learning.

Robert H. Crabtree, Organometallic Chemistry of the Transition

Metals, 5th edition (2009).

D. Astruc, Organometallic Chemistry and Catalysis, Springer (2007).

STUDENT FEEDBACK ON MODULE

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Solutions to quizzes and tests will be pasted on Blackboard and, optionally,
on the notice board. Highlights on problematic areas will be discussed in
class during some lectures.

MODULE POLICY (Including plagiarism, academic honesty,

attendance etc.)
Attendance: By registering for this module, you made a commitment to
attempt all of the work that may be assigned. Attendance is not mandatory,
but you will find that punctual and regular attendance is vital for carrying out
this commitment. Moreover, cutting classes (for whatever reason) shows a
lack of respect for your fellow students and your lecturer.

Academic Integrity: Honesty and integrity are key qualities that are
encouraged not only in the Department of Chemistry, but across the
University of Limpopo. You are, therefore, expected to be fully aware of your
responsibility to maintain a high quality of integrity in all your work. Cheating
of any form will not be tolerated!

Tutorial-type Quiz: A tutorial-type quiz will be pasted on Blackboard every

second week, with the due date indicated. Please take the quizzes seriously
for a good module mark.

ADDITIONAL MODULE INFORMATION

N/A

TENTATIVE SCHEDULE OF LECTURES

Date Topic/Activity
29/03/2023 Recap on SCHB021 outcomes
29/03/2023 Rules of Valence: The EAN Rule
31/03/2023 Bonding in Coordination Compounds: VBT
05/04/2023 Bonding in Coordination Compounds: CFT
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12/04/2023 Consequences of the CFT: Spectrochemical Series
14/04/2023 Bonding in Coordination Compounds: MOT
19/04/2023 π-Acceptor Ligands
21/04/2023 Organometallic Compounds: Conjugated pi-systems
26/04/2023 Organometallic Compounds: Metallocene Bonding
03/05/2023 Organometallic Compounds: Metallocene Reactions
05/05/2023 Test 2
10/05/2023 The Isolobal Analogies
12/05/2023 Homogeneous Catalysis
17/05/2023 f-Block Elements: Configurations & trends

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 TUTORIAL QUESTIONS

Some of the tutorials in this course are a recap on the work covered in SCHB021,
but important for this module as well. Students are strongly encouraged to revise
the work, solve the problems and discuss the solutions with the lecturer if they
feel uncertain.

Tutorial 1

1. How would you define a transition element? List the properties associated with
transition elements.

2. Explain giving reasons why:

(i) Most of the transition metals are paramagnetic

(ii) Compounds of transition metals are generally coloured

(iii) All transition metals exhibit variable oxidation states.

3. Explain the following terms:

(i) Coordination compound (ii) Complex (iii) Ligand (iv) Bidentate (v) Ambidentate (vi)
Chelate (vii) π-acceptor and π-donor ligands (viii) Hemilabile ligands.

4. How would you determine the coordination number of a metallic atom or ion in a
complex?

5. What fraction of the chlorines in [Co(NH3)4Cl2]Cl can be titrated by aqueous silver

nitrate? Explain. [7]

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 Tutorial 2

1. Write the coordination number and the oxidation number for the central atom or ion
and also the IUPAC names for the following:

(a) [Co(NH3)2(NO2)4]- , (b) [Cr(NH3)5Cl]Cl2, (c) K4[Fe(CN)6], (d) [Pd(NH3)4]2+.

(b) (i) (NH4)3[Cr(SCN)6]; (ii) (NH4)2[Pt(NCS)6]; (iii) [(NH3)]5Co–NH2–Co(NH3)5](NO3)5; (iv)

[(NH3)]5Co–NH2–Co (NH3)5]Cl5; (v) [Fe2(CN)10(μ-CN)]5−; (v) [Fe2(CO)6(μ-CO)3]; (vi)
[{Co(NH3)4}2(μ-Cl)(μ-OH)]4+;

2. What do you understand by the terms inner- and outer-orbital complexes as used in
valence bond theory (VBT)?

3. Why are the dz2 and dx2-y2 orbitals utilized in d2sp3 and sp3d2 hybridisation rather than
two of the dxy, dyz and dxz orbitals?

4. Using the valence bond theory, describe the bonding in [Fe(CN)6]3–. Identify whether
it is an inner or outer orbital complex.

5. Differentiate between outer orbital complexes and inner orbital complexes.

Tutorial 3

1. Calculate the CFSE, crystal field stabilization energy for d2, d3, d4, d6 octahedral high-
spin and low-spin complexes.

2. Explain the following terms:

(i) High-spin, low-spin complexes (ii) Spectrochemical series (iii) Pairing energy (iv)
crystal field stabilization energy (v) Jahn Teller distortion (vi) Paramagnetism (vii) Molar
susceptibility (viii) diamagnetism (ix) paramagnetism (x) Spin-only magnetic moment.

The spectrochemical series:

I- < Br- < SCN- < Cl- < F- ≤ OH- , ONO- < OH2 < NCS- < NCCH3 < NH3, py <
NO2- < CN- , NO , CO
weak-field ligands strong-field ligands

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3. The magnetic moment of the complex [Mn(NCS)6]4- is 6.06 μB. What is its d-electron
configuration in terms of t2gx egy?

4. An aqueous solution of zinc nitrate contains the [Zn(OH2)6]2+ ion and is colourless.
Explain these observations. [6]

5. Differentiate between a normal spinel and an inverse spinel.

6. Use the CFSE as a criterion to classify the following spinels as normal or inverse:

(a) Fe3O4 (b) Co3O4 (c) NiFe2O4 (d) ZnCr2O4

7. Define the term octahedral site stabilization energy (OSSE).

Tutorial 4

1. What is an organometallic compound?

2. Count the valence electrons in the following compounds:

(a) [IrBr2(CH3)(CO)(PPh3)2] (b) [V(CO)6] (c) [W(CH3)6]

(d) [Cr(η5-C5H5)(CO)2(PPh3)] (e) [Mn(CO)5]

3. Discuss the two principal methods of synthesis of metal carbonyls.

4. Give the formal name of ferrocene. Which are the two important reactions that
ferrocene can undergo? Describe the bonding in ferrocene.

5. Describe associative and dissociative mechanisms as encountered in transition

metal complexes.

6. The complex [Cr(CO)4(PPh3)2] has one very strong IR absorption band at 1889 cm-1
and two other very weak bands in the CO stretching region. What is the probable
structure of this compound?

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 Tutorial 5

1. The IR spectrum of [Ni2(η5-Cp)2(CO)2] has a pair of CO stretching bands at 1857

cm-1 and 1897 cm-1. Does this complex contain bridging or terminal CO ligands, or
both?

2. Explain the following terms:

(a) Hapticity (b) Eighteen electron complexes (c) Tolman’s cone angle (d) Fischer
carbenes (e) migratory insertion reaction.

3. Define the terms (a) catalyst, (b) catalyst cycle, (c) catalyst support, (d) turnover
frequency, (e) selectivity, (f) homogeneous catalysis.

4. Addition of PPh3 to a solution of Wilkinson’s catalyst, [RhCl(PPh3)3], reduces the

turnover frequency for the hydrogenation of propene. Give a plausible mechanistic
explanation for this observation.

5. The rates of hydrogen absorption (in dm3 mol-1 s-1) by alkenes catalysed by
[RhCl(PPh3)3] in benzene at 25 oC are: hexane, 2910; cis-4-methyl-2-pentene, 990;
cyclohexene, 1360; 1-methyl-cyclohexene, 60. Suggest the origin of the trends and
identify the affected reaction step in the proposed mechanism (Fig. 26.5 in Atkins,
Overton, Rourke, Weller and Armstrong, 5th Edition).

6. An increase in CO partial pressure above a certain threshold decreases the rate of

cobalt-catalysed hydroformylation of 1-pentene. Suggest an interpretation of this
observation.

7. Describe the mechanism for the hydroformylation of 1-butene to pentanal using a

cobalt carbonyl complex as catalyst.

Tutorial 6

1. Describe the Monsanto acetic acid synthesis using a diagram.

2. Describe the Wacker process (oxidation of alkenes).

3. Draw and discuss the catalytic cycle for the hydrogenation of an alkene by
Wilkinson’s catalyst.

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4. Explain the following terms:

(a) Migratory insertion (b) oxidative addition (c) reductive elimination (d)
hydrocarbonylation, (e) Migratory insertion, (f) β-hydride elimination.

5. State Tolman’s rules for supplementing the 18-electron rule.

Tutorial 7

1. Define the lanthanide contraction.

2. Briefly describe the causes and consequences of the lanthanide contraction.

3. By means of a flow-chart, show how lanthanide ions can be extracted from their
ores.

4. Briefly discuss ion-exchange chromatography as a tool for separating lanthanide

ions after extraction, including the various equilibria involved. Draw a fully labelled free-
hand diagram to illustrate the eluted products.

5. Describe the coordination chemistry of lanthanides. What are the common

coordination numbers?

6. How do the optical spectra of lanthanide complexes compare with their transition
metal counterparts?

7. What are the everyday uses of lanthanides?

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