Tutorial Letter 101/3/2020: Inorganic Chemistry III
Tutorial Letter 101/3/2020: Inorganic Chemistry III
Tutorial Letter 101/3/2020: Inorganic Chemistry III
Semesters 1 and 2
Department of Chemistry
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CONTENTS
Page
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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.
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.
2.2 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.
3.2 Department
Department of Chemistry
College of Science, Engineering & Technology
Eureka Building, Block K- M 042
[email protected]
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 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.
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.
It is advisable to have contact with fellow students. One way to do this is 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.
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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CHE3701/101/3/2020
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.
Syllabus:
Topic 1. An introduction to coordination compounds
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Topic 5. Introductory d-metal organometallic chemistry
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CHE3701/101/3/2020
SEMESTER 2
Assignment 01: Unique No: 692238
Assignment 02: Unique No: 631789
Assignment 03: Unique No: 629115
SEMESTER 2
Assignment 01: 07 August 2020
Assignment 02: 28 August 2020
Assignment 03: 18 September 2020
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To submit an assignment via myUnisa:
Go to myUnisa.
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.
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CHE3701/101/3/2020
SEMESTER 1
Assignment 01
COMPULSORY
Questions to be answered
Question 1
a) Define the following terms. Illustrate your answer with a suitable diagram.
(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
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
Question 4
a) [Co(py)2(SCN)2]
b) [Mn(en)2(H2O)]2+
Question 5
a) Draw an energy level diagram illustrating allowed , and n-electron transitions observed
in UV-Vis spectroscopy.
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.
TOTAL [100]
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Assignment 02
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.
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
b) Discuss the differences between Ligand Field Theory and Crystal Field Theory. Illustrate
your answer with suitable diagrams.
Question 4
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.
TOTAL [100]
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Assignment 03
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:
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.
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
COMPULSORY
Questions to be answered
Question 1
a) Define the following terms. Illustrate your answer with a suitable diagram.
(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
Question 4
a) [Ni(CN)2(H2O)2]
b) [Mn(acac)2Br2]2-
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Question 5
TOTAL [100]
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Assignment 02
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.
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
b) Predict the products of the following square planar substitution reactions. Explain your
answer. Draw the predicted structures.
Question 5
a) Consider the following reaction:
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.
TOTAL [100]
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Assignment 03
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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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.
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
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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