Download CH 4950 - Loyola College

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)
01. What is slipped Sandwich? Cite an example.
02. Define coordination template effect. Cite a dinuclear complex synthesized by
the method.
03. Justify the formation of coordination compounds of different geometries by d
block metal ion with the help of angular overlap model.
04. What is tetragonal splitting parameter? How is it evaluated?
05. Differentiate CE and EC mechanisms.
06. Give the structure of (a) Potassium ethylxanthate
(b) Dipheylphosphinoethane (dppe).
07. How are he optical isomers of [Co (NH3)4 Cl2]+ distinguished?
08. [NiCl4]2- has a magnetic moment of 2.84 B.M. Predict the geometry with
hybridization of the metal atom.
09. 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+ .  EQ of the former is zero and the later has a  EQ value of 3.3 mm s-1.
18. Suggest a method of synthesis for
(a) [Co (NH3)6]Cl3 from CoCl2.6H2O
(b) Cis and trans  [Pt(NH3)2Cl2]
(2)
(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.
(b) 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 Dqxy and Dqz values.
(b) How is spin crossover studied experimentally?
(c) 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.
(b) 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.
(b) How does Cr(CO)6 undergo photochemical decomposition?
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