CHE3701/102/0/2024

Tutorial Letter 102/0/2024

Inorganic Chemistry (III) Theory

CHE3701

Year Module

Chemistry Department

IMPORTANT INFORMATION
Please register on myUnisa, activate your myLife e-mail account and
make sure that you have regular access to the myUnisa module
website, CHE3701-2024-0, as well as your group website.

Note: This is a fully online module. It is, therefore, only available on myUnisa.

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1. ASSESSMENT

1.1 Assessment due dates

• There are no assignment due dates included in this tutorial letter.

• Assignment due dates will be made available to you on the myUnisa landing page for this
module. We envisage that the due dates will be available to you upon registration.

• Please start working on your assessments as soon as you register for the module.

• Log on to the myUnisa site for this module to obtain more information on the due dates
for the submission of the assessments.

1.2 Submission of assessments

• Unisa, as a comprehensive open distance e-learning institution (CODeL), is moving

towards becoming an online institution. You will therefore see that all your study material,
assessments and engagements with your lecturer and fellow students will take place
online. We use myUnisa as our virtual campus.

• The myUnisa virtual campus will offer students access to the myModules site, where
learning material will be available online and where assessments should be completed.
This is an online system that is used to administer, document, and deliver educational
material to students and support engagement between academics and students.

• The myUnisa platform can be accessed via https://my.unisa.ac.za. Click on the

myModules 2024 button to access the online sites for the modules that you are
registered for.

1.3 The assessments

As indicated in Tutorial Letter 101 you need to complete 06 formative assessments for this
module. The contribution of each assessment to your year mark is as follows:

Assessment 1 - Assignment 01 (15%)

Assessment 2 - Assignment 02 (15%)

Assessment 3 - Assignment 03 (15%)

Assessment 4 - Assignment 04 (15%)

Assessment 5 - Quiz (10%)

Assessment 6 - Essay/Portfolio (30%)

1.3.1 Assignment 01
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The assignment covers:

Topic 1: An introduction to coordination compounds
Topic 2: Physical techniques used in coordination chemistry
Before attempting this assignment work through Learning Units 1 and 2 from the Study Guide
and Chapters 20 and 21 from the course textbook.

NOTE: All diagrams, chemical structures and illustrations must be hand-drawn.

Start each question on a new page.

Number your answers as per the question.
Number your pages.

Questions to be answered.

Question 1

a) Define the following terms. Illustrate your answer using a metal complex which explains
your answer.

(i) HSAB principle

(ii) Bidentate ligand
(iii) Chelate effect
(iv) Bite angle
(v) Hydrate isomerism

b) Draw the structure of each of the following complexes. Clearly show the stereocentre of
central metal ion. Where multiple geometric isomers are possible, draw both.

(i) [Fe(SCN)4(H2O)2]2-

(ii) [Co(en)2Cl2]Cl

(iii) [Ni(NH3)4(C2O4)2]·H2O

c) Give the systematic name for each of the following complexes:

(i) [Fe(SCN)4(H2O)2]2-
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 (ii) [Co(en)2Cl2]Cl

(iii) [Ni(NH3)4(C2O4)2]·H2O

Question 2

a) The octahedral complex [(Co(NH3)6]3+ absorbs light with a wavelength of 420

nm. Calculate the splitting energy Δ for this complex. Show all calculations.

b) Consider the Ti(II) ion

(i) Using the corresponding Tanabe-Sugano diagram, give the free-ion ground
state term symbol.
(ii) Draw the d-electron configuration of the Ti(II) ion in an octahedral symmetry.
Label the orbital sets.
(iii) Using the corresponding Tanabe-Sugano diagram, give term symbol
corresponding to this configuration.
(iv) Briefly explain why a high-spin configuration is not possible for an octahedral Ti(II)
complex in the ground state.
(v) List the electron transitions expected for the [Ti(H2O)6]2+ ion.
(vi) Give the free-ion d-electron configuration corresponding to the term symbol 1D,
the first excited state for Ti(II).

Question 3

a) Consider the following two cobalt complexes:

[Co(H2O)2(OH)4] [Co(CO)6]3+
Complex A Complex B

(i) Draw the d-electron configuration for A and B. Label each set of orbitals.
(ii) Explain how the d-electron configuration changes when cobalt is replaced by iridium
in A and B.
(iii) Calculate the CFSE for A and B. Show all calculations and units.
(iv) Which of these two complexes (A or B) will interact with a magnet? Motivate your
answer.

Question 4

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For each of the following complex ions:

a) [NiBr4]2-

b) [Ni(acac)2(CN)2]2-

(i) Determine the oxidation state of the metal

(ii) Give the coordination number of the metal ion
(iii) Draw the d-orbital electron configuration
(iv) Calculate the CFSE in units of o or T

Each question carries 25 marks.

TOTAL [100]

1.3.2 Assignment 02

This assignment covers:

Topic 3: Electronic structures and properties of d-metal coordination complexes

Topic 4: Reactions and mechanisms of coordination complexes
Before attempting this assignment work through Learning Units 3 and 4 from the Study Guide
and Chapters 20 and 21 from the course textbook.

NOTE: All diagrams, chemical structures and illustrations must be hand-drawn.

Start each question on a new page.

Number your answers as per the question.
Number your pages.

Questions to be answered.

Question 1

a) The 4-coordinate complex ion [AgCl4]1- is diamagnetic, whereas [CuCl4]1- is

paramagnetic.
(i) Use the magnetic behaviour of these complexes to determine the geometric structure
of each ion. Illustrate your answer with suitable electron configuration and structure
diagrams for both species.

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 (ii) Briefly discuss why these two complex ions adopt different geometries.

Question 2

a) The spin-only magnetic moment (eff) of an octahedral Mn(II) complex is 5.92 BM.
Determine its d-electron configuration. Show all calculations.

b) Briefly explain why the complex ion [Fe(H2O)6]2+ is attracted to a magnet and [Fe(CN)6]4-
is not. Illustrate your answer with suitable diagrams.

c) The rate constants for the formation of [Co(NH3)5X]2+ from [Co(NH3)6]3+ differs by less
than a factor of 2 when X = Cl–, Br –
or SCN–. Predict the mechanism of the reaction.
Explain your answer and illustrate with a suitable mechanism scheme.

Question 3

a) State the Jahn-Teller Theorem

b) Draw the d-orbital splitting diagram for a complex in an octahedral field which exhibits:
(i) Tetragonal compression Jahn-Teller distortion.
(ii) Tetragonal elongation Jahn-Teller distortion.
Label each orbital in your diagram.

c) Which of the following complexes would show strong Jahn-Teller distortion:

(i) [Fe(H2O)6]3+
(ii) [Co(CN)6]3-
(iii) [Ni(C2O4)3]
Motivate your answer with d-orbital splitting diagrams.

Question 4

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

(i) transition state

(ii) reaction intermediate
(iii) inert complex
(iv) labile ligand

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b) Give a multi-step synthesis method for the preparation of trans [Pt(NH3)2(PPh3)Cl]+

starting from [PtCl4]2-. Show all the reaction steps in the synthesis and illustrate your
answer with line drawings clearly showing the stereochemistry at the metal centre.

Each question carries 25 marks.

TOTAL [100]

1.3.3 Assignment 03

This assignment covers:

Topic 5: Introductory d-metal organometallic chemistry

Before attempting this assignment work through Learning Units 5 and 6 from the Study Guide
and Chapters 22 and 26 from the course textbook.

NOTE: All diagrams, chemical structures and illustrations must be hand-drawn.

Start each question on a new page.

Number your answers as per the question.
Number your pages.

Questions to be answered.

Question 1

a) Draw the structure and give the systematic name of the organometallic complexes:
(i) [Fe(CO)4Br2]

(ii) [Ti(5-C5H5)2Cl2]
(iii) [Mo(CO)2(PMe3)4]

(iv) [Rh(6-C6H6)(2-C2H4)2]+
(v) [Fe2(CO)9]

b) Give the d-electron count (use the neutral ligand counting method) of the following
complexes:
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 (i) [Fe(CO)4Br2]

(ii) [Ti(5-C5H5)2Cl2]
(iii) [Mo(CO)2(PMe3)4]

(iv) [Rh(6-C6H6)(2-C2H4)2]+
(v) [Fe2(CO)9]

Question 2
a) Briefly describe the metal-carbonyl bond using the Dewar-Chatt-Duncanson model.
Illustrate your answer with suitable diagrams. Show each bonding component separately
and orbital phases must be clearly indicated.

b) Explain the trend in the IR stretching frequency, v(CO), for the metal carbonyl complexes
below:

Metal Carbonyl Complex v(CO) cm‐1

[Ti(CO)6]2- 1748

[Mn(CO)6]+ 2100

[Fe(CO)6]2+ 2204

Question 3
a) (i) Draw the structure of bis(η4-cycloocta-1,5-diene)nickel.
(ii) What is the hapticity of the cyclooctadiene (cod) ligand?
(iii) What is the oxidation state of the metal?
(iii) Briefly describe the bonding between Ni and the cod ligand.

b) Consider the acetylacetonate (acac) ligand and answer the following questions:
(i) Draw the structure of the acac ligand.
(ii) Identify all the donor atoms of the ligand.
(iii) What is the denticity of the ligand?
(iv) What is the charge of the ligand?
(v) Draw the structure of an octahedral cobaltate complex with two acac chelating
ligands and two L-type ligands. Clearly show the geometry at the metal centre.
(vi) Identify the oxidation state of the central metal ion in the structure drawn in (v).

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Question 4
Briefly describe the following types of reactions:
a) Oxidative addition
b) Reductive elimination

c) -Hydrogen elimination
d) Alkyl migration
Illustrate your answer with a suitable chemical reaction.

Each question carries 25 marks.

TOTAL [100]

1.3.4 Assignment 04

This assignment covers:

Topic 6: Introductory bio-inorganic chemistry

Before attempting this assignment work through Learning Units 5 and 6 from the Study Guide
and Chapters 22 and 26 from the course textbook.

NOTE: All diagrams, chemical structures and illustrations must be hand-drawn.

Start each question on a new page.

Number your answers as per the question.
Number your pages.

Questions to be answered.

Question 1

a) What are the chemical properties of platinum complexes that make them suitable as
anticancer drugs?

b) Using a Pt(IV) complex, briefly discuss how photoactivation is used to generate an active
drug.

Question 2
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a) Draw the structure of the following platinum complexes which are used to treat cancer.
(i) Cisplatin
(ii) Satraplatin
b) Briefly discuss the difference between the two complexes.
c) Briefly discuss the anticancer mode of action of Satraplatin.

Question 3

a) Draw the following conformations of ferrocene:

(i) Staggered
(ii) Eclipsed

b) Draw the structures of:

(i) Chloroquine
(ii) Ferroquine

c) Define the term ansa-metallocene.

d) Draw the structure of modified Ferroquine with chloroquine in an ansa arrangement.

Question 4

a) Draw the structure of the following gold complexes which are used to treat rheumatoid
arthritis.
(i) Myochrisin
(ii) Allochrysine
(iii) Sanochrysin

b) Briefly discuss the similarities in structure of the three complexes.

c) Using HSAB theory, predict how the stability of the complex would change if the S-donor
ligand was changed to an Se-donor ligand. Motivate your answer.

Each question carries 25 marks

TOTAL [100]

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1.3.5 Quiz

The quiz will be available on the course website.

1.3.6 Essay/Portfolio

Choose one of the following topics to write a literature review report.

1. Hemoglobin versus Chlorophyll: A Comparison of Structure and Activity

2. Application of Silicon Dioxide in Solar Cells

3. Gold Nanoparticles in Medicine

4. The Mode of Action of Cisplatin as an Anticancer Drug

Literature Review Report Guidelines:

The paper should be typed and include the following sections: Title, Abstract (or Summary),
Introduction, Results (from the literature), Major Findings, Conclusions and Future Outlook. The
report should be approx. 10 pages, with 1.5 line spacing using 12 point Arial font. The report
should include: Figures, Schemes and a References Section. Figures may be used from journal
articles, however these must be acknowledged in your captions and cited in your references.
Use the Royal Society of Chemistry referencing format. A reference guide is available on the
course website. Books and journal articles (with doi) should be cited, websites should not be
cited.

Refer to the UNISA Policy on Plagiarism. A TURNITIN report for this assignment is
MANDATORY. Submit your report as a PDF document, together with the TURNITIN report as a
single document. You will receive a mark of zero for this assignment if a TURNITIN report is not
submitted.

TOTAL [100]

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