INDIAN INSTITUTE OF TECHNOLOGY, KHARAGPUR

Department of Chemistry
End Spring Semester Examination 2011-2012

Time: Three hours. Maximum Marks: 50 No. of Students: 13 + 43 = 54

4th Year oflntegrated M. Sc. and 1st year ofM.Sc.-Ph.D. Course
Sub. Name & No. CY41010- Introduction to Bioinorganic Chemistry
CY41006 - Principles to Organometallic Chemistry
CY41014- Principles of Organometallic and Bioinorganic Chemistry

Instruction: Use two separate answer books for Part A and Part B. Answer to all parts
of one question must be given at one place only.

Part A: Organometallics

1) Describe the bonding models for Pt(PPh3hC2H4 and Pt(PPh3h(C2CN4). 2 marks

2) Write the structure of A and B.

9>'
oc'''''
Mo
! "'co
co
PhCH 2CI
------!~ A
hv
------!~ B

2 marks

3) Write resonance forms for a Fischer carbene complex. 1 mark

1
4) The compound A gives only one signal, doublet, for its terminal CH 2 protons in the H
NMR spectrum, explain why? What is A?

2 marks
5) Write two sources of NO using which nitrosyl complexes can be prepared. 1 marks
6) Arrange the following ligands in an increasing order of n-acidity: PCI 3, CO, P(OMeh,
PMe 3, PF 3. Rationalize your answer. 1 mark
7) Predict ifthe following complexes will undergo ~-elimination or not and rationalize your
answer. 1 mark

TitQ) 4

1
 8) Carbonyl stretching frequencies of the oxidative addition products from Vaska's
complex are given below.

Reagent v(CO), ~v(CO),

cm- 1 cm~ 1
None 1967 0
Oz 2015 48
HCl 2046 79
CzF4 2052 85
Clz 2075 108
~v increases on going from the top to bottom in the above Table, Why? 2 marks
9) Write the concerted mechanism for the oxidative addition of H2 to the Vaska's complex.
2 marks
10} Write the decarbonylation products with percentage for this reaction. Explain why?

COMe
oc;, ,, ~~co -CO
'~.Mri''
oc~ I ~co
co 2 marks
11) Write the products A and B formed in the below reaction

R R'
Md + ~ ____.. A --J)Ioo~ B 2 marks
12) Write the structure of A and B.

co
A .. ,,.. B
0 2 marks
13} Write the synthesis for Tebbe's reagent and the product formed upon its reaction with
an ester. 2 marks
14) Arrange v(CO} values of the j..t3 -CO, terminal CO, free CO, and ~-trCO in a decreasing
order. Explain why? 1 mark
15) Write the product for this reaction: 2 marks

Q>,,Fe~,,,cH3
oc'''' A ··'''
co
H3C H

I 2

!
 Part B: Bioinorganic Chemistry

Answer all THREE questions.

1. a) Ribonucleotide reductase (RR) catalyzes the conversion of ribonucleotides to

deoxyribonucleotide di- or triphosphates.
Explain the catalytic reaction involved in it. Compare the Fe2 site present in RR to
that present in Hemerythrin.

·b) Explain the use of rigid face capping N-donor ligands to synthesize diiron model
complexes in any coordination chemistry laboratory.
[5+3]

2. a) What are ferredoxin dependent enzymes? Explain magnetic, EXAFS and structural
detail of the following rubredoxin center involved in the reduction of superoxide
anion to H202.

b) Identify the two classes of ferredoxin molecules and the formal oxidation numbers
of the iron ions from the following scheme.

[5+3]

3. a) What is metalloexopeptidase? Explain H+ shift from ghu-270 to tyr-248 in it.

b) Compare the coordination environments around the metal ion in (i) carbonic
anhydrase, (ii) alcohol dehydrogenase, (iii) thermolysin and (iv) ,8-lactamase.
c) Explain how methylcobalamin plays an important role in the environment.

[3+3+3]

Paper ends here