LOYOLA COLLEGE (AUTONOMOUS), CHENNAI – 600 034

LM 42

M.Sc. DEGREE EXAMINATION – CHEMISTRY

THIRD SEMESTER – APRIL 2007

CH 3802 – COORDINATION CHEMISTRY

 

 

 

Date & Time: 28/04/2007 / 9:00 – 12:00      Dept. No.                                       Max. : 100 Marks

 

Part – A

Answer all the questions                                                                  (10 x 2 = 20)

 

1. What are inert and labile complexes?
2. What is chelate effect? Explain with an example.
3. What is the ground term of a free ion with 3d⁹ configuration?
4. What are π-acceptor ligands? Give two examples.
5. Explain Why do the bond order values of C-O in mixed phosphine carbonyls vary in the order [(Ph₃P)₃Mo(CO)₃] < [(Cl₃P)₃Mo(CO)₃].
6. Why are the magnetic moment of Co(II), high spin, octahedral complexes much higher than that of tetrahedral complexes?
7. Explain S_N¹CB mechanism with an example.
8. Why is MnO₄^– ion, a d⁰ system coloured?
9. What is meant by hapticity of a ligand? How is it designated?
10. Differentiate the types of cytochromes.

 

Part – B

Answer any eight  questions                                                          (8 x 5 = 40)

 

1. Explain the geometry of [Fe(H₂O)₆]²⁺ and [Fe(CN)₆]^4- ions using VB theory.
2. How does M.O theory explain the field strength of Cl^– and CN^–.
3. State and explain Jahn-teller theorem. Discuss the consequences of Jahn-Teller distortions on the electronic spectra of octahedral complexes.
4. How is optical rotatory dispersion study useful to determine the absolute configuration of chiral complexes.
5. Explain the EPR spectral features of Cu^II(salen) complex.
6. What is trans effect? Discuss the theories of trans effect.
7. Explain the types of  photosubstitution reactions of metal complex with examples.
8. Explain the fluxional isomerism with two examples.
9. Explain the synergic effect of metal-ligand bonding in metal carbonyls.
10. 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- .
11. Predict the structure of the following using Wade’s Rule. a) Os₅(CO)₁₆  b)Re₄(CO)₁₆^2-.
12. Describe the essential structure of haemoglobin and explain the cooperativity in its oxygenation.

 

 

 

Part – C

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

 

1.  Explain the splitting of degeneracy of d-orbitals in square planar environments of ligands.
2.  Discuss the bonding in ferrocene on the basis of molecular orbital energy level diagram.
3.  Explain the features of Tanabe- Sugano and Orgel diagrams. Construct Orgel diagram for d³and d⁷, tetrahedral and octahedral complexes.
4. a) Explain the principles involved in the Mossbauer spectral analysis of metal complexes.

1. b) How do the Mossbauer spectra of K₄[Fe(CN)₆] and K₃[Fe(CN)₆] differ.

1. Discuss in detail the mechanisms of outer and inner sphere electron transfer in metal complexes.
2.  Write short notes on

1. a) Wilkinson catalyst b) Zeigler-Natta catalyst
2. c) Wacker’s process d) Fischer Tropsch process

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