LOYOLA  COLLEGE (AUTONOMOUS), CHENNAI-600 034.

M.Sc. DEGREE  EXAMINATION  – chemistry

fourth  SEMESTER  – APRIL 2003

CH  4950/CH 1054 ADVANCED COORDINATION  chemistry 

23.04.2002

1.00 – 4.00                                                                                          Max: 100 Marks

 

part – A                                                       (10 ´ 2 = 20)

 

1. What is slipped Sandwich?   Cite an example.
2. Define coordination template effect. Cite a dinuclear complex synthesized by

the method.

3. Justify the formation of coordination compounds of different geometries by d-

block metal ion with the help of angular overlap model.

4. What is tetragonal splitting parameter? How is it evaluated?
5. Differentiate CE and EC mechanisms.
6. Give the structure of (a) Potassium ethylxanthate

(b) Dipheylphosphinoethane (dppe).

7. How are he optical isomers of [Co (NH₃)₄ Cl₂]⁺ distinguished?
8. [NiCl₄]^2- has a magnetic moment of 2.84 B.M. Predict the geometry with hybridization of the metal atom.
9. How are the complexes [Cr(NH₃]₄ Cl₂]Cl and [Cr(NH₃)₃Cl₃] distinguished by NQR spectroscopy?
10. What role is  played by cisplatin in the cancer therapy?

 

PART- B                                           (8 ´ 5 = 40 Marks)

 

11. Explain the principles of angular overlap model.
12. What are compartmental ligands? Explain the different methods of syntheizing compartmental ligands and their polynuclear complexes.
13. Explain the electronic spectral features of high-spin octahedral and tetrahedral complexes.
14. Give an account of spectroelectrochemical techniques in studying electrogenerated species.
15. Explain the principle of AC polarography. How is this technique useful to study the reversible redox couples?
16. Explain with an example the experimental method of studying static dynamic Jahn-Teller effect.
17. Explain that the isomer shift value of [Fe (CN)₆]^4– is more negative than that of

[Fe (H₂O)₆]²⁺ . D E_Q of the former is zero and the later has a D E_Q value of 3.3 mm s^-1.

 

 

 

 

 

18. Suggest a method of synthesis for

(a) [Co (NH₃)₆]Cl₃ from CoCl₂.6H₂O                                                                                     (2)

(b) Cis and trans – [Pt(NH₃)₂Cl₂]                                                               (1 ½  + 1 ½)

 

19. Discuss the different sampling methods used in EPR spectroscopy. Bring out their advantages.
20. How do the quantum yields vary in a photoanation reactions? Discuss with a suitable example.
21. Discuss the coordination around iron in cytochrome and the role played by it in the biological processes.
22. How is N(1s) photoelectron spectrum useful in the study of [Co(NH₃)₅ N₃](NO₃)₂

 

PART – C                                         (4 ´10 = 40 Marks)

 

23. (a) Derive the Marcus-Hush equation for electron transfer.

• Explain how do the crystal field effect influence the rate of electron

transfer reactions.

24. (a) Explain the electronic spectral features of  low -spin d⁶ metal ion and

the  method of computing Dq^xy and Dq^z values.

• How is spin crossover studied experimentally?
• Give an account of NMR spectra of paramagnetic compounds.

 

26. Discuss the role played by the metal atoms in the Nitrogen fixation. Write a note

on  biomimic coordination. cluster complexes of nitrogenase.

 

27. (a) Explain the  Mossbauer spectrum of FeF₃ recorded at 4K.                         (5)

• Describe Krammer’s degeneracy choosing an example.

 

28. (a) Discuss in detail the EPR spectrum of [Cu (salimine)₂] along with the

hyperfine splitting by the ligand.                                                                 (7)

 

(b)   How does Cr(CO)₆ undergo photochemical decomposition?                      (3)

 

 

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