1

THE UNIVERSITY OF THE WEST INDIES

ST. AUGUSTINE

EXAMINATIONS OF APRIL/MAY 2008

Code and Name of Course: CHEM 3167 (C30A) – ADVANCED INORGANIC CHEMISTRY

Date and Time: Duration: Two (2) hours

INSTRUCTIONS TO CANDIDATES: This paper has Five (5) pages and Six (6) questions

ATTEMPT ANY FOUR (4) QUESTIONS

TOTAL VALUE OF PAPER = 100 MARKS

The use of non-programmable calculators is permitted.

TRACER CHARTS AND CHARACTER TABLES ARE PROVIDED

PERIODIC TABLE OF THE ELEMENTS

1 2
H He
3 4 5 6 7 8 9 10
Li Be B C N O F Ne
11 12 13 14 15 16 17 18
Na Mg Al Si P S Cl Ar
19 20 21 22 23 24 25 26 27 28 29 30 31 32 33 34 35 36
K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr
37 38 39 40 41 42 43 44 45 46 47 48 49 50 51 52 53 54
Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe
55 56 57 72 73 74 75 76 77 78 79 80 81 82 83 84 85 86
Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn
87 88
Fr Ra

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code C30A 2007/2008/…….

___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……

 Page 2

1. The water molecule (H2O) belongs to the C2v symmetry point group.

(a) Identify the valence orbitals on the central O atom in the H2O molecule. (3 marks)

(b) Assign the valence orbitals you identified in (a) to symmetry species explaining how you
made your assignments. (5 marks)
(c) Deduce the allowed Terminal Atom Symmetry Orbitals (TASOs) for the peripheral H
atoms stating any rules you used. (4 marks)
(d) Draw a labeled Molecular Orbital Energy Level diagram for the H2O molecule. (8 marks)

(e) Deduce:

(i) the total number of valence electrons in the H2O molecule and fill them into the

diagram you drew in (d). (3 marks)

(ii) the O⎯H bond order. (2 marks)

2. The BF3 molecule belongs to the D3h symmetry point group.

(a) Identify the valence orbitals on the central B atom in the BF3 molecule. (3 marks)

(b) Using the character tables provided, assign as many of the valence orbitals on the B atom

as you can to symmetry species. (2 marks)

(c) Now assign any remaining valence orbitals on the B atom to symmetry species explaining

how you made your assignments. (4 marks)

(d) Deduce the allowed Terminal Atom Symmetry Orbitals (TASOs) for the peripheral

F atoms. (5 marks)

(e) Sketch the allowed 2pz and 2py TASOs for the peripheral F atoms. (6 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code C30A 2007/2008/…….

___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……

 Page 3

Question 2 (continued)
(f) The following is a partial Molecular Orbital Energy Level Diagram for the BF3 molecule
A1'*

E'*

2px, 2py
2px
A2', E', A2", E", A2"
2pz 2py
2pz
E

2s

E'

A1'

E' 2s TASOs
A 1'

B F TASOs

(i) Determine the total number of valence electrons in the molecule. (2 marks)

(ii) Sketch a representation of this diagram in your answer booklet and fill these electrons

into your diagram. (3 marks)

3. (a) Draw the structure of the complex cation [Fe(diars)2Cl2]+ in the trans-dichloro configuration

[diars = o-phenylene-bis-(dimethylarsine)]. (5 marks)

(b) Use an energy level diagram to show the expected electronic configuration of iron in octahedral

[Fe(diars)2Cl2]+. (5 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code C30A 2007/2008/…….
___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……

 Page 4

Question 3 (continued)
(c) Detailed structural analysis of [Fe(diars)2Cl2]+ reveals a tetragonally distorted coordination
mode. How are the energy levels and electronic spin of iron likely to be different?
(8 marks)
Would you expect the complex cation to be stable in strong acid if the iron is oxidized to
a tetravalent state? Explain. (7 marks)

4. (a) In processing iron, what is the Bessemer conversion? (5 marks)

(b) Briefly describe the properties of the transition elements which account for their widespread
use as catalysts (10 marks)

(c) In the presence of hydrogen gas, a combination of Ni[P(OEt)3]4 and H2SO4 will effect

isomerization of alkenes. Show the steps leading to the rearrangement of the double bond.

(10 marks)

5. (a) The allyl ligand, C3H5, can attach to a transition metal through one carbon atom (η1) or
through all three carbon atoms (η3).

(i) Assuming that both complexes obey the 18-electron rule, deduce the values of x and y
in [Fe(η1-C3H5)(η5-C5H5)(CO)X] and [Co(η3-C3H5)(CO)Y]. Show your reasoning.
(8 marks)
(ii) Describe how spectroscopic methods could be used to determine whether an allyl

ligand was bonded η1 or η3 to a metal. (5 marks)

(iii) The η3-allyl complex [(η3-MeCHCHCH2)Mn(CO)4] can exist in 2 isomeric forms.

Use a diagram to explain why. (5 marks)

PLEASE TURN TO THE NEXT PAGE

© The University of the West Indies Course Code C30A 2007/2008/…….

___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……

 Page 5

Question 5 (continued)
(b) The compounds Mo(C6H6)2 and Ru(C6H6)2 each contain two benzene rings coordinated
to a central metal atom. Explain why the room temperature proton decoupled 13C NMR
spectrum of the Mo complex shows a single peak at 75.4 ppm but that of the Ru complex
shows four peaks at 47.2, 68.7, 72.1 and 130.8 ppm in the approximate ratio 2:2:6:2.
(7 marks)

6. For each of the following mixtures of reactants, give (i) a plausible chemical equation and
(ii) the structure for the organometallic product, and (iii) a general reason for the course of the
reaction:
(a) Ru3(CO)11(PMe3) and 2 moles of PMe3;
(b) Phenyllithium and Mo(CO)6;
(c) (OC)5Cr=CPh(OMe) and NHEt2;
(d) MeMn(CO)5 and 1 mole of PMe3;
(e) (η6-C6H5Cl)Cr(CO)3 and NaOMe. (5 x 5 marks)

END OF EXAMINATION PAPER

© The University of the West Indies Course Code C30A 2007/2008/…….

___________________________________________________________________________________________________________

DO NOT WRITE OR TYPE ON THE BACK OF THIS SHEET: USE ONE SIDE ONLY

INSTRUCTIONS: Each page must be signed by the Examiners and where applicable, the University Examiner and/or
the External Examiner. Where the examination does not require a University Examiner, the form must be signed by the First
and Second Examiners. Completed forms should be handed to the Assistant Registrar (Examinations). The EXTERNAL
EXAMINER is requested to sign the question paper and return it with comments, it any, (on a separate sheet), to the Assistant
Registrar (Examinations).

……………………………………. ……………………………………..
First Examiner University Examiner

…………………………………… …………………………………….
Second Examiner External Examiner (where applicable)

Date: 20…/…../….. Date: 20…../……/……