INDIAN INSTITUTE OF TECHNOLOGY, KHARAGPUR

Department of Chemistry
Mid Spring Semester Examination 2012-2013

Time: Three hours Maximum Marks: 25 (Part A) + 25 (Part B) = 50

Number of Students: 17 + 39 = 56
~ubject code/Name: CY410 14/Principles of Organometallics and Bioinorganic Chemistry

Instructions: Separate answer scripts are to be used for Part A and Part B. Answer all the
questions from Part A and Part B. Answers to all parts of every question must be given
consecutively.

PART A

1. Explain the following terms:

(a) Nonclassical carbonyl complex
(b) Cone angle of phosphine ligands
(c) Oxophilic or fluorophilic 3 marks

Nu-
----•~ No reaction 2 marks
3
[(11 -C3Hs)Mo(C0)2Cp] does not undergo a reaction with nucleophiles (Nu-). What is the
reaction strategy to make this molecule to be reactive toward nucleophiles? Explain

3. Which is a better n-acceptor, PF 3 or P(OMe)3? Rationalize with a MO diagram.

2 marks
4. Write the structure of A and Bin the following reaction.
2-

CI-Pd-CI
.f'i + A
Base
... B
cf 2 marks

2 marks

6. Write the structure of A and B in the following reaction. What type of complex is B?

LiNEt2
Fe(C0) 5 ,._.
2 marks

7. Give the oxidation states, cf configurations and valence electron counts for the
following: (a) [(11 -CsHs)MoBr(N0)(11 3-CJHs)] (b) [(11 5-CsHs)Fe(ll 6-C 6H 6)t
5
4 marks

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8. Allyl complexes are fluxional . .Explain the dym(mic process of exchange of syn and artti
substituenfs .and sketch the expected 1H NMR spectra recorded at low and high
temperatures.
3,marks
9. · What is A and .B in t!)e following reaction? Write a. plaiJsible mechanism for the
fonnation ofA and .B.

(OC) 5 W OMe
~-- ...
, ~, A + B
Ar
2,marks

10. Predict the products "of the addition of PMeJ to the complex shown below, show
~tructure of e<;1ch complex and their expected relative distributions.
Me
ock r
'''Mri''
,,\co
Me~P.,-. } ~co
PM'e3

3 marks

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 PARTB

1. (a) Though Cu is abundant in sea-water, it was not involved at the early stage of life
evolution. Give plausible reasons. 1 mark

· 2. "Explain the origin of cooperativity of 0 2 binding with the hemoglobin. Show the steps
with mentioning structural change. 2 marks

3. (a) Between 0 2-· and ol- which one is more toxic? (b) How would you distinguish
spectroscopically between the superoxide ion and the peroxide ion? (c) In biological 02-
activating centres (such as Fe-herne, Fe-nonheme, Type III Cu-proteins, cytochrome c
oxidases etc.) have two interacting redox centres (2 metals or 1 metal + 1 n system).
Suggest plausible reasons. 1+1+ 1=3 marks

4. (a) How does nature protect Fe(II) in Hb from irreversible oxidation in the presence of
0 2? (b) What is picket-fence model of Fe-porphyrin, and how does it protect Fe(II)
centre from irreversible oxidation? 1+2=3 marks

5. (a) Show the active centre of deoxy- and oxy-hemocyanin (Oxidation states,
coordination, ligands and geometry should be mentioned). (b) Mention color and its
origin for the both forms. (c) Why does paramagnetic 30 2 bind very rapidly with
diamagnetic deoxy-hemocyanin? (d) Why oxy-hemocyanin is diamagnetic although it
has Cu2+ centres? 1.5+ 1.5+ 1+1=5 marks

6. (a) Why does nature not use the porphyrin ligand in Vitamin B12, although Co2+/3+ forms
stable complex with porphyrin ligand? (b) Draw the structure of alkyl cobalamin
(clearly show oxidation state on metal, geometry around metal centre and the ligands).
(c) Show all the alternatives of Co-c cleavage in alkyl cobalamin with resultant
eliminated alkyl ligands and the produced metal centres. Among the produced metal
centres which one could be regarded as "super-nucleophile"? 1+2+3=6 marks

7. (a) What is "superoxide dismutaion reaction"? (b) Draw the active site of Cu,Zn-SOD
(c) Suggest the reasons for having the active site in a funnel-shaped deep channel. (d)
Comment the role of Zn centre in Cu,Zn-SOD. 1+ 1+ 1+1=4 marks

8. Between deoxy- and oxy-hemerythrins, in which case magnetic susceptibly is higher and
why? 1 mark

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