LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

M.Sc. DEGREE EXAMINATION – CHEMISTRY

GH 56

THIRD SEMESTER – APRIL 2008

CH 3802/ 921 – COORDINATION CHEMISTRY

 

 

 

Date : 29-04-08                  Dept. No.                                        Max. : 100 Marks

Time : 1:00 – 4:00

 

Part – A

Answer all the questions                                                                  (10 x 2 = 20)

 

1. What are polydentate ligands? Give an example.
2. What is the ground term of 3d⁷ configuration?
3. Why the magnetic moment of Co(II) octahedral complexes are much higher than that of tetrahedral complexes?
4. Explain why CrO₄^2- ion with d⁰ configuration is coloured?
5. What are Π-acceptor ligands? Give two examples.
6. Explain S_N¹CB mechanism with an example.
7. What is meant by hapticity of a ligand? How is it designated?
8. Differentiate the types of cytochromes.
9. What are cryptands? Mention any one application.
10. What is Wilkinson catalyst? What type of reaction can make use of this catalyst?

 

Part – B

Answer any eight questions                                                      (8 x 5  = 40)

11. What is tetragonal distortion? Which dⁿ configurations lead to strong Jahn teller distortion in octahedral and tetrahedral complexes?
12. What are the basic postulates of valence bond theory? How does valence bond theory explain the geometry and magnetic properties of (i) [Co(NH₃)₆]³⁺ and (ii) [CoF₆]^3-
13. Explain how optical rotatory dispersion study is useful to determine the absolute configuration of chiral complexes.
14. Discuss the bonding in ferrocene on the basis of molecular orbital energy level diagram.
15. Explain the variations in the stretching frequency of the isoelectronic species, Cr(CO)₆, V(CO)₆^– and Mn(CO)₆⁺.
16. Explain the trans effect in the substitution reactions of square planar complexes.
17. Explain the fluxional isomerism with two examples.
18. Explain the crystal structures of Fe₃O₄, ZnFe₂O₄ as spinel or inverse spinel
19. Explain the synergic effect of metal-ligand bonding in metal carbonyls.
20. Apply Wade’s rule to predict the geometry of

a)[Fe₅(CO)₁₅C]         b) [h⁵C₅H₅RhFe₃(CO)₁₁]

21. Briefly explain the significances of metal complexes in nitrogen fixation
22. Write short notes on
23. a) Wacker’s process b) Fischer Tropsch process

 

Part – C

Answer any four questions.                                                          (4 x 10 = 40)

23. Explain the d orbital spilitting of square planar complexes using crystal field theory. Why does the metal ion with d⁸ configuration in a strong field form square planar complexes?
24. Explain Why Cl^– acts as a weak ligand whereas CN^– acts as strong ligand in octahedral transition metal complexes with the help of MO theory.
25. Explain the features of Tanabe- Sugano and Orgel diagram. Construct orgel diagram for d³and d⁷, tetrahedral and octahedral complexes.
26. Explain the principles involved in the Mossbauer spectral analysis of metal complexes and explain how do the Mossbauer spectra of K₄[Fe(CN)₆] and K₃[Fe(CN)₆] differ.
27. a) Discuss in detail the mechanisms of outer and inner sphere electron transfer in metal complexes.                                                                                  (10)
28. b) Why is the electron transfer in the system [Co(NH₃)₆]²⁺ – [Co(NH₃)₆]³⁺ slower than that in the system [Fe(CN)₆]^4- and [Fe(CN)₆]^3- .                        .
29. Describe the essential structure of haemoglobin and explain its cooperativity in its oxygenation.

 

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