CHE3701/101/3/2020

Tutorial Letter 101/3/2020

Inorganic Chemistry III

CHE3701

Semesters 1 and 2

Department of Chemistry

This tutorial letter contains important information

about your module.

BARCODE
 CONTENTS

Page

1 INTRODUCTION TO THE MODULE ............................................................................................ 3

2 PURPOSE AND OUTCOMES ...................................................................................................... 3
2.1 Purpose ........................................................................................................................................ 3
2.2 Outcomes ..................................................................................................................................... 3
3 LECTURER(S) AND CONTACT DETAILS.................................................................................... 4
3.1 Lecturer ........................................................................................................................................ 4
3.2 Department ................................................................................................................................... 4
3.3 University ...................................................................................................................................... 4
4 RESOURCES ............................................................................................................................... 5
4.1 Prescribed book(s) ........................................................................................................................ 5
4.2 Recommended book(s) ................................................................................................................. 5
4.3 Electronic reserves (e-reserves) ................................................................................................... 6
5 STUDENT SUPPORT SERVICES ................................................................................................ 7
6 STUDY PLAN ............................................................................................................................... 7
7 PRACTICAL WORK ..................................................................................................................... 8
8 ASSESSMENT ............................................................................................................................. 9
8.1 Assessment criteria....................................................................................................................... 9
8.2 Assessment plan .......................................................................................................................... 9
8.3 Assignment numbers .................................................................................................................. 11
8.3.1 General assignment numbers ..................................................................................................... 11
8.3.2 Unique assignment numbers ...................................................................................................... 11
8.4 Assignment due dates ................................................................................................................ 11
8.5 Submission of assignments ........................................................................................................ 11
8.6 The assignments ........................................................................................................................ 12
8.7 Other assessment methods ........................................................................................................ 28
8.8 The examination ......................................................................................................................... 28
9 FREQUENTLY ASKED QUESTIONS ........................................................................................ 28
10 SOURCES CONSULTED ........................................................................................................... 28
11 IN CLOSING ............................................................................................................................... 28
12 ADDENDUM ............................................................................................................................... 28

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 CHE3701/101/3/2020

Dear Student

As part of this tutorial letter, we wish to inform you that Unisa has implemented a transformation
charter based on five pillars and eight dimensions. In response to this charter, we have also
placed curriculum transformation high on the agenda. For your information, curriculum
transformation includes the following pillars: student-centred scholarship, the pedagogical
renewal of teaching and assessment practices, the scholarship of teaching and learning, and
the infusion of African epistemologies and philosophies. These pillars and their principles will be
integrated at both the programme and module levels, as a phased-in approach. You will notice
the implementation thereof in your modules, and we encourage you to fully embrace these
changes during your studies at Unisa.

1 INTRODUCTION TO THE MODULE

We are pleased to welcome you to this module (CHE3701) and hope that you will find it both
interesting and rewarding. We shall do our best to make your study of this module successful.
You will be well on your way to success if you start studying early in the semester and resolve to
do the practical work properly.

2 PURPOSE AND OUTCOMES

2.1 Purpose
The purpose of this course is to guide students in the understanding of the fundamental
concepts of electronic structure and spectra in d-metal complexes and coordination compounds
and apply these concepts and methods to an understanding of the role of coordination and
organometallic compounds in catalysis, materials chemistry and bioinorganic chemistry.

2.2 Outcomes

The students will be introduced to the basic theoretical principles of electronic structure and
spectra of d-metal complexes. An application of this knowledge into organometallic chemistry
and its applications in material science are envisaged.

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The students will be given the opportunity to apply their knowledge and skills gained to practical
situations in advanced inorganic chemistry.

3 LECTURER(S) AND CONTACT DETAILS

3.1 Lecturer
The lecturer responsible for this module is
Lecturer’s name: Prof HS Clayton
Department of Chemistry
College of Science, Engineering & Technology
Eureka Building, Block K- M 028
clayths@unisa.ac.za
011 670 9310

3.2 Department
Department of Chemistry
College of Science, Engineering & Technology
Eureka Building, Block K- M 042
chemistry@unisa.ac.za
011 670 9318/9327

3.3 University
Communication with the University
If you need to contact the University about matters not related to the content of this module,
please consult the publication Study@Unisa that you received with your study material. This
booklet contains information on how to contact the University (e.g. to whom you can write for
different queries, important telephone and fax numbers, addresses and details of the times
certain facilities are open). Always have your student number at hand when you contact the
University.

PLEASE NOTE: Letters to lecturers may not be enclosed with or inserted into
assignments.

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 CHE3701/101/3/2020

4 RESOURCES
4.1 Prescribed book(s)

The Prescribed textbook for CHE3701 is:

Title: Inorganic Chemistry, 7th edition
Authors: Mark Weller, Tina Overton, Jonathan Rourke, Fraser Armstrong
Publisher: Oxford University Press
ISBN: 9780198825906

The previous edition of the textbook may also be used:

Title: Inorganic Chemistry, 6th edition
Authors: Peter Atkins, Mark Weller, Tina Overton, Jonathan Rourke, Fraser Armstrong
Publisher: Oxford University Press
ISBN: 9780199641826

The University does not provide copies of this book. Students are expected to obtain their own
copies. As most of the study material for this module is included in this book, it is essential to
have access to a copy of the textbook. You may use the fourth and fifth edition as well if you are
unable to get hold of the prescribed edition. However, note that the page numbers and
arrangement of the chapters is different.

4.2 Recommended book(s)

The following are publications that you may consult in order to broaden your knowledge of
inorganic chemistry.
S.F.A. Kettle, Physical inorganic chemistry: A coordination approach, Oxford University Press.
F.A. Cotton, G. Wilkinson and P.L. Gaus, Basic Inorganic Chemistry, John Wiley and Sons.
B. Douglas, D. McDaniel and J. Alexander, Concepts and Models of Inorganic Chemistry, John
Wiley and Sons.
J. E. Huheey, Inorganic Chemistry: Principles of Structure and Reactivity, Harper and Row.
The following books are useful reference books:
J.C. Bailar, H.J. Emeléus, R. Nyholm and A. F. Trotman-Dickenson (eds.), Comprehensive
Inorganic Chemistry (5 Volumes), Pergamon Press.
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F. A. Cotton and G. Wilkinson, Advanced Inorganic Chemistry, John Wiley and Sons.
N. N. Greenwood and A. Earnshaw, Chemistry of the Elements, Pergamon Press.
G. Wilkinson, R.D. Gillard and J. A. McCleverty (eds.), Comprehensive Coordination Chemistry
(5 Volumes), Pergamon Press.

Recommended books can be requested online, via the library catalogue.

4.3 Electronic reserves (e-reserves)

There are no e-reserves for this module.
E-reserves can be downloaded from the library catalogue. More information is available at:
http://libguides.unisa.ac.za/request/request

4.4 Library services and resources information

The Unisa Library offers a range of information services and resources:

 for brief information go to: https://www.unisa.ac.za/library/libatglance

 for more detailed Library information, go to
http://www.unisa.ac.za/sites/corporate/default/Library
 for research support and services (e.g. Personal Librarians and literature
search services), go to
http://www.unisa.ac.za/sites/corporate/default/Library/Library-
services/Research-support

The Library has created numerous Library guides: http://libguides.unisa.ac.za

Recommended guides:

 request and find library material/download recommended material:

http://libguides.unisa.ac.za/request/request
 postgraduate information services:
http://libguides.unisa.ac.za/request/postgrad
 finding and using library resources and tools:
http://libguides.unisa.ac.za/Research_skills
 Frequently asked questions about the Library: http://libguides.unisa.ac.za/ask
 Services to students living with disabilities:
http://libguides.unisa.ac.za/disability

Important contact information:

 https://libguides.unisa.ac.za/ask - Ask a Librarian

 Lib-help@unisa.ac.za - technical problems accessing library online services
 Library-enquiries@unisa.ac.za - general library related queries
 Library-fines@unisa.ac.za - for queries related to library fines and payments
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 CHE3701/101/3/2020

5 STUDENT SUPPORT SERVICES

The Study@Unisa brochure is available on myUnisa: www.unisa.ac.za/brochures/studies
This brochure has all the tips and information you need to succeed at distance learning and,
specifically, at Unisa.

If you have access to a computer that is linked to the internet, you can quickly access resources
and information at the University. The myUnisa learning management system is Unisa's online
campus that will help you to communicate with your lecturers, with other students and with the
administrative departments of Unisa – all through the computer and the internet.

To go to the myUnisa website, start at the main Unisa website, http://www.unisa.ac.za, and then
click on the “Login to myUnisa” link on the right-hand side of the screen. This should take you to
the myUnisa website. You can also go there directly by typing in http://my.unisa.ac.za.

Please consult the publication Study@Unisa which you received with your study material for
more information on myUnisa.

Discussion classes
No Discussion Classes are scheduled for CHE3701.

Contact with fellow students

It is advisable to have contact with fellow students. One way to do this is to form study groups.

See myUnisa Discussion forum to form study groups.

6 STUDY PLAN
The myUnisa Learning Management System

The myUnisa Learning Management System is the online campus network that enables each
student to communicate via the internet with academic staff, fellow students and the
administrative departments within UNISA. Students can also access resources and information
from the university.

Use the Study@Unisa brochure for general time management and planning skills.

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7 PRACTICAL WORK
Practical work forms an essential part of CHE3701. Students are required to attend a
compulsory practical course during Semester 2 of 2020.

All the prescribed practical work will be carried out during this period. You have to register for
the compulsory practical Module CHE3721. Full details of this practical course, venue and
the procedures will be given in a special Tutorial letter CHE3AL-F/101/2020.

7.1 ADMISSION TO PRACTICALS

Students registered for the Inorganic Chemistry practical module, CHE3721 will be required to
submit one compulsory assignment for this module. On passing this assignment (minimum
50%), a student will be admitted to attend the practical course in Semester 2 of 2020.

7.2 PRACTICAL WORK AT OTHER UNIVERSITIES

Students who are unable to attend the laboratory course at the scheduled time may do the
practicals at another university. Such students have to request approval from the Head of
Department of Chemistry at UNISA to ascertain whether a particular practical course will be
accredited by UNISA. However, gaining access to a specific institution is solely the
responsibility of the student. Exemptions from any of the third level chemistry modules is not
allowed.

Applications for exemption from practical work must be made in writing and directed to:
The Chair of Department
Department of Chemistry
Private Bag X 6
UNISA
Florida Campus
1710

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8 ASSESSMENT
8.1 Assessment criteria
Students' knowledge of topics of inorganic chemistry covered in the course will be assessed by
a written examination (80%) and three written assignments (20%). The student is expected to
present a sound understanding of the major concepts and theoretical principles in inorganic
chemistry outlined in the syllabus below as well as demonstrate the ability to solve basic
problems in inorganic chemistry in an accurate manner.

The main content of this class is a review on the basic inorganic chemistry principles and
theories as outlined in the syllabus in 8.2 below.

NOTE: Although students may work together when preparing assignments, each student must
write and submit his or individual assignment. In other words, you must submit your own ideas
in your own words, sometimes interspersing relevant short quotations that are properly
referenced. It is unacceptable for students to submit identical assignments on the basis that
they worked together. That is copying (a form of plagiarism) and none of these assignments will
be marked. Furthermore, you may be penalized or subjected to disciplinary proceedings by the
University.

8.2 Assessment plan

Assignments are seen as part of the learning material for this module. As you do the
assignment, study the reading texts, consult other resources, discuss the work with fellow
students or tutors or do research, you are actively engaged in learning. During your learning
process you should also consult with your lecturer who will clarify some concepts in order to
prepare you for the assignments. Looking at the assessment criteria given for each assignment
will help you to understand what is required of you more clearly.

Syllabus:
Topic 1. An introduction to coordination compounds

Topic 2. Physical techniques used in coordination chemistry

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

Topic 4. Reactions and mechanisms of coordination complexes

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Topic 5. Introductory d-metal organometallic chemistry

Topic 6. Introductory bio-inorganic chemistry

Topic 1: An introduction to coordination compounds

Chapter 6 Coordination chemistry nomenclature

Constitution and geometry
Isomerism and chirality

Topic 2: Physical techniques used in coordination chemistry

Chapter 8 Absorption and emission spectroscopies
Resonance techniques
Magnetometry and magnetic susceptibility

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

Chapter 20 Electronic structure
Electronic spectra

Topic 4: Reactions and mechanisms of coordination complexes

Chapter 21 Ligand substitution reactions
Ligand substitution in square planar complexes
Ligand substitution in octahedral complexes

Topic 5: Introductory d-metal organometallic chemistry

Chapter 22 Organometallic chemistry nomenclature
Electron counting and oxidation states
Ligands in organometallic complexes

Topic 6: Introductory bio-inorganic chemistry

Chapter 26 Inorganic chemistry in medicine

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8.3 Assignment numbers

8.3.1 General assignment numbers
Assignments are numbered consecutively per module, starting from 01.

8.3.2 Unique assignment numbers

SEMESTER 1
Assignment 01: Unique No: 555273
Assignment 02: Unique No: 537909
Assignment 03: Unique No: 675077

SEMESTER 2
Assignment 01: Unique No: 692238
Assignment 02: Unique No: 631789
Assignment 03: Unique No: 629115

8.4 Assignment due dates

SEMESTER 1
Assignment 01: 13 March 2020
Assignment 02: 03 April 2020
Assignment 03: 24 April 2020

SEMESTER 2
Assignment 01: 07 August 2020
Assignment 02: 28 August 2020
Assignment 03: 18 September 2020

8.5 Submission of assignments

You may submit written assignments either by post or electronically via myUnisa. Assignments
may not be submitted by fax or e-mail. For detailed information and requirements as far as
assignments are concerned, see the brochure Study@Unisa that you received with your study
material.

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To submit an assignment via myUnisa:

 Go to myUnisa.

 Log in with your student number and password.

 Select the module.

 Click on assignments in the left-hand menu.

 Click on the assignment number you want to submit.

 Follow the instructions on the screen.

NOTE: Do not submit your assignment as a read-only or password protected pdf document.
These files cannot be marked on the online system. Proofread your submission to ensure all
pages have been included.

8.6 The assignments

Assignments are seen as part of the learning material for this module. As you do the
assignment, study the reading texts, consult other resources, discuss the work with fellow
students or tutors or do research, you are actively engaged in learning. During your learning
process you should also consult with your lecturer who will clarify some concepts in order to
prepare you for the assignments. Looking at the assessment criteria given for each assignment
will help you to understand what is required of you more clearly.

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 CHE3701/101/3/2020

SEMESTER 1

Assignment 01

Due Date: 13 March 2020 Unique no: 555273

COMPULSORY

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 6 and 8 from the course textbook.

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

Questions to be answered

Question 1

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

(i) Ambidentate ligand

(ii) Monodentate ligand
(iii) Chelate
(iv) Hydration shell (of an ion)
(v) Orbital degeneracy

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

(i) [Co(NH3)4(NO2)F][NO3]

(ii) K[Cr(ox)2(H2O)2]

(iii) [Pt(bpy)Cl2]·H2O

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c) Draw the structure of each of the following complexes. Clearly show the stereocentre of
the central metal ion.
(i) [Co(NH3)4(NO2)F]NO3

(ii) K[Cr(ox)2(H2O)2]

(iii) [Pt(bpy)Cl2]·H2O

Question 2

a) State the Jahn-Teller Theorem

b) Draw the d-orbital splitting diagram for complex in an octahedral field. Label each orbital.

c) Draw the d-orbital splitting diagram for complex in an octahedral field which exhibits
Jahn-Teller distortion. Label each orbital.

Question 3

a) Draw all possible isomers of [Co(py)2(SCN)2], a tetrahedral complex.

Clearly show the stereocentre of the central metal ion.

b) Draw all possible isomers of [Mn(en)2(H2O)]2+, an octahedral complex.

Clearly show the stereocentre of the central metal ion.

Question 4

For each of the following complex ions:

a) [Co(py)2(SCN)2]

b) [Mn(en)2(H2O)]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

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Question 5

a) Draw an energy level diagram illustrating allowed ,  and n-electron transitions observed
in UV-Vis spectroscopy.

b) Which transition has the highest energy?

c) Which transition absorbs light with the highest frequency? Explain your answer.

d) Which transition absorbs light with the highest wavelength? Explain your answer.

e) Explain why the highest energy transitions are not measured in UV-Vis spectrometry.

Each question carries 20 marks.

TOTAL [100]

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Assignment 02

Due Date: 03 April 2020 Unique no: 537909

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.

Questions to be answered

Question 1

a) For the Mn3+ ion determine the ground state (free-ion) term symbol. Show how the
ground state term symbol would split in octahedral symmetry.

b) Using the appropriate Tanabe-Sugano Diagram, predict the spin-allowed electronic

transitions for [Mn(H2O)6]3+.

c) The complex [Mn(H2O)6]3+ absorbs light with a wavelength of 460nm. Determine the
splitting energy . Show all calculations. Give your answer in units of cm-1.

Question 2

a) The spin-only magnetic moment (eff) of an octahedral Co(II) complex is 3.87 BM. Draw
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) For the Fe(II) ion determine the ground state term symbol. Show how the ground state
term symbol would split in octahedral symmetry. List the transitions expected for
[Fe(H2O)6]2+.
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Question 3

a) Discuss the limitations of Valence Bond Theory regarding coordination complexes.

b) Discuss the differences between Ligand Field Theory and Crystal Field Theory. Illustrate
your answer with suitable diagrams.

Question 4

a) Define the terms:

(i) transition state

(ii) reaction intermediate

b) Use the trans-effect series to design synthetic routes for the following complexes from
[PtCl4]2- :

(i) cis-[Pt(NH3)(NO2)Cl2]-

(ii) trans-[Pt(NH3)(NO2)Cl2]-

Question 5

a) Explain why is the hydrolysis of [Co(NH3)5Cl]2+ in the presence of base much faster than
that of [Co(py)5Cl]2+?

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

Each question carries 20 marks.

TOTAL [100]

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Assignment 03

Due Date: 24 April 2020 Unique no: 675077

This assignment covers:

Topic 5: Introductory d-metal organometallic chemistry

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.

Questions to be answered

Question 1

a) Draw the structure and the systematic name of the following d-metal complexes:
(i) [Mn(CH3)3(PMe3)3]
(ii) [Fe(C5H5)2]
(iii) [Co(CO)4Br]
(iv) [Pt(C2H4)Cl3]
(v) [Mn(CO)5]2

b) Give the d-electron count (use the neutral ligand counting method) of the following
complexes:
(i) [Mn(CH3)3(PMe3)3]
(ii) [Fe(C5H5)2]
(iii) [Co(CO)4Br]
(iv) [Pt(C2H4)Cl3]
(v) [Mn(CO)5]2

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Question 2
The infrared stretching frequency of CO gas is 2143cm -1. The CO stretching frequency of some
d- metal carbonyl complexes are given below:

[Mn(CO)6]+ 2090 cm-1

[Cr(CO)6] 2000cm-1
[V(CO)6]- 1866cm-1
[Ti(CO)6]2- 1750 cm-1

a) Using the Dewar-Chatt-Duncanson model explain why these stretching frequencies differ
from that of CO gas. Illustrate your answer with a suitable diagram.

b) Explain the trend in (CO) in the complexes listed above.

Question 3
a) (i) Draw the structure of [Cr(CO)3(C6H6)]
(ii) What is the coordination number of the Cr ion?
(iii) What is the hapticity of the C6H6 ligand?
(iv) Briefly describe the bonding between Cr and C6H6. Illustrate your answers
with a suitable diagram.

b) Which of the following complexes would be stable or unstable? Explain your answer.

(i) [Fe(CO)4(NO)]
(ii) [Co(CO)3(NO)]
(iii) [Ni(CO)3(NO)]
(iv) [Fe(CO)3(NO)2]

Question 4
a) Draw the structure of the following platinum based anticancer complexes:
(i) Cisplatin
(ii) Carboplatin
(iii) Oxaliplatin
(iv) Nedaplatin

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b) Briefly discuss the mechanism of action of Cisplatin. Illustrate your answer with suitable
diagrams.
Each question carries 25 marks.

TOTAL [100]

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 CHE3701/101/3/2020

SEMESTER 2

Assignment 01

Due Date: 07 August 2020 Unique no: 692238

COMPULSORY

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.

Questions to be answered

Question 1

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

(i) HSAB principle

(ii) Polydentate ligand
(iii) Chelate effect
(iv) Bite angle
(v) Denticity

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

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

(ii) [Cr(en)2Cl2][SO4]

(iii) [Rh(NH3)4(ONO)2]·3H2O

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c) Draw the structure of each of the following complexes. Clearly show the stereocentre of
central metal ion.
(i) [Fe(ONO)4(H2O)2]2-

(ii) [Cr(en)2Cl2][SO4]

(iii) [Rh(NH3)4(ONO)2]·3H2O

Question 2

a) For the following complexes predict which ones would have Jahn-Teller distortion.
Illustrate with suitable your answer diagrams.

(i) [Ti(NH3)6]3+

(ii) [Cr(NH3)6]2+

(iii) [Cu(H2O)6]2+

(iv) [Ni(NH3)6]2+

Question 3

a) Draw all possible isomers of [Ni(CN)2(H2O)2], a tetrahedral complex.

Clearly show the stereocentre of the central metal ion.

b) Draw all possible isomers of [Mn(acac)2Br2]2-, an octahedral complex.

Clearly show the stereocentre of the central metal ion.

Question 4

For each of the following complex ions:

a) [Ni(CN)2(H2O)2]

b) [Mn(acac)2Br2]2-

(i) Determine the oxidation state of the metal

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(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

Question 5

Consider the UV-Vis spectrum of 1,3-butadiene given below:

a) Determine the approximate value of max from the spectrum.

b) Assign the electron transition which gives rise to the absorbance band observed. Explain
your answer.
c) Based on the spectrum above, predict the colour of 1,3-butadiene. Explain your answer.
d) Explain why the absorbance bands observed in UV-Vis spectra are broad and not well-
defined (sharp).
e) Draw a general schematic of the layout of a typical UV-Vis spectrophotometer.

Each question carries 20 marks.

TOTAL [100]

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Assignment 02

Due Date: 28 August 2020 Unique no: 631789

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.

Questions to be answered

Question 1

a) For the Co2+ ion determine the ground state (free-ion) term symbol. Show how the
ground state term symbol would split in octahedral symmetry.

b) Using the appropriate Tanabe-Sugano Diagram, predict the spin-allowed electronic

transitions for [Co(H2O)6]2+.

c) The complex [Co(H2O)6]2+ absorbs light with a wavelength of 585nm. Determine the
splitting energy . Show all calculations. Give your answer in units of cm-1.

Question 2

a) The spin-only magnetic moment (eff) of an octahedral Mn(III) complex is 4.90 BM. Draw
its d-electron configuration. Show all calculations.

b) The complex ion [Ni(CN)4]2- is diamagnetic, whereas [NiCl4]2- is paramagnetic. Use the
magnetic behaviour of these complexes to determine the geometric structure of each ion.
Illustrate your answer with suitable diagrams.

c) For the Cr(I) ion determine the ground state term symbol. Show how the ground state
term symbol would split in octahedral symmetry. List the transitions expected for
[Cr(en)2(CN)2]1-.

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Question 3
a) Discuss and compare the following bonding theories: (i) valence bond theory, (ii) crystal
field theory and (iii) ligand field theory. Include in your discussion a comparison of the
strengths and weaknesses of each theory.

Question 4
a) Define the terms:

(i) trans-effect

(ii) trans influence

b) Predict the products of the following square planar substitution reactions. Explain your
answer. Draw the predicted structures.

(i) [Pt(NO2)Cl3]2- + NH3 →

(ii) cis-[Pt(py)2(NH3)2]2+ + 2Cl - →

Question 5
a) Consider the following reaction:

[MLnCl] – + Br – → [MLnBr] – + Cl–

Given the following information: an intermediate complex with a charge 2- forms and
the rate constant changes by a factor of 117 if iodide is used instead of bromide

(i) Predict the overall reaction mechanism. Illustrate your answer with a suitable
diagram.

(ii) Predict the value of n in [MLnCl] –

Each question carries 20 marks.

TOTAL [100]

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Assignment 03

Due Date: 18 September 2020 Unique no: 629115

This assignment covers:

Topic 5: Introductory d-metal organometallic chemistry

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.

Questions to be answered

Question 1

a) Draw the structure and the systematic name of the following d-metal complexes:
(i) [Mn(CO)3H3]
(ii) [Ti(C5H5)2Cl2]
(iii) [Cr(CO)5(PPh3)]

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

b) Give the d-electron count (use the neutral ligand counting method) of the following
complexes:
(i) [Mn(CO)3H3]
(ii) [Ti(C5H5)2Cl2]
(iii) [Cr(CO)5(PPh3)]

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

Question 2
a) A compound with empirical formula Fe2(C5H5)2(CO)4 exhibits carbonyl stretching
frequencies at 1780 and 2000 cm-1. Draw the structure of the compound and assign the
(CO) stretches in the structure.

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 CHE3701/101/3/2020

b) The CN- ligand can act as a σ donor and a π acceptor. The σ donor orbital is anti-
bonding with respect to the C–N bond. Given that the (CN) stretching frequency in the
IR spectrum of [Pt(CN)4]2- is 2170 cm-1 while free CN-exhibits (CN) at 2080 cm-1, which
property, σ donation or π acceptance dominates in this complex? Provide a clear
explanation of your reasoning.

Question 3
a) (i) Draw the structure of [Co(CO)2(NO)(cot)] where cot is cyclooctatriene.
(ii) What is the coordination number of the Co ion?
(iii) What is the hapticity of the cot ligand?
(iv) Briefly describe the bonding between Co and cot.

b) Which of the following complexes would be stable or unstable? Explain your answer.
(i) [Fe(CO)3]
(ii) [Fe(CO)6]
(iii) [Fe(NO)5]
(iv) [Fe(CO)2(NO)2]

Question 4
a) Draw the structure of the following antimalarial complexes:
(i) Chloroquine
(ii) Ferroquine
b) Briefly discuss the effect of the iron group in Ferroquine. Illustrate your answer with
suitable diagrams.
Each question carries 25 marks.

TOTAL [100]

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8.7 Other assessment methods
There are no other assessment methods for this module.

8.8 The examination

Consult the brochure Unisa: services and procedures which you received with your study
material. The examination paper for CHE3701 will be 2 hours. Your year mark counts 20% and
your exam mark 80% of your final mark. The university requires that a sub-minimum of 40%
must be achieved in the examination to pass the module.

Supplementary examination

If your final mark (taking the semester mark into account) is between 40% and 49%, you will be
given an opportunity to rewrite the examination in the next examination period. This means that
if you are registered for the first semester, you will write the examination in May/June 2020 and
the supplementary examination will be written in October/November 2020. If you are registered
for the second semester, you will write the examination in October/November 2020 and the
supplementary examination will be written in May/June 2021

9 FREQUENTLY ASKED QUESTIONS

None.

10 SOURCES CONSULTED
Inorganic Chemistry: Principles of Structure and Reactivity; J. E. Huheey; Harper and Row.
Inorganic Chemistry, 5th edition; C.E. Housecroft, A.G. Sharpe; Pearson.

11 IN CLOSING
I hope that you will enjoy this module and wish you success with your studies.
Kind regards.

12 ADDENDUM
None.
©
UNISA 2020

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