*PG317*

PG – 317

III Semester M.Sc. Degree Examination, January 2013 (2006-07 Onwards) (R.S.) CHEMISTRY C-302-AC : Reaction Mechanism, Catalysis and Organometallic Chemistry Time : 3 Hours

Max. Marks : 80

Instruction : Answer question 1 and any five of the remaining. Answer any ten of the following :

(10×2=20)

1. a) Give an example for a non-complementary electron transfer reaction. Why are these reactions generally slow ? b) Octahedral Cr(III) complexes are generally inert towards substitution reactions. Give reasons. c) Substitution reactions in square planar complexes proceed in a SN 2 mechanism. Justify. d) Give the reaction profiles for A, D and I mechanism. e) Give the mechanism involved in the production of ethylene glycol from synthesis gas. f) Enumerate the industrial importances of oxo process. g) What are the industrial requirements of catalysis ? h) Give the IUPAC nomenclature of the following : i) Mg Br [CH (CH3)2] ii) [Pt Cl2 (C2H4) (NH3)] i) Transition metals with higher atomic number having d8 configuration generally prefer square planar 16 e configuration. Why ? j) Explain oxidative addition reaction with a suitable example. P.T.O.

PG – 317

-2-

*PG317*

k) Determine the metal-metal bond order consistent with the 18 electron rule for the following : i) [( η 5 – C5H5) Fe (CO)2]2 ii) [ η 5 – C5H5 M8 (CO)2]2 l) Explain the reactivity of [Al F6]3 – , SiF62– , PF6– and SF6 in basic aqueous medium. 2. a) Give Taube’s explanations of labile and inert complexes. Classify the following as labile or inert [Mn (H2O)6]2+ , [Fe (H2O)6]2+ , [V (H2O)6]2+ and [Ni (en) 3]2+ . b) Discuss SN1CB mechanism for the base hydrolysis of Co(III) octahedral complex. c) Discuss the mechanism of CO insertion into [CH3 Mn (CO)5] complex. (4+4+4 = 12) 3. a) What is chelate effect ? How does this affect the rate of substitution in octahedral complex ? b) Differentiate between outer sphere and inner sphere mechanism with suitable examples and expalin the role of bridging ligand in inner sphere mechanism. c) What is trans effect ? Describe electrostatic polarisation theory of trans effect. (4+4+4 = 12) 4. a) Discuss briefly on the thermodynamic and kinetic aspects of catalysis. b) With the help of catalytic cycle, discuss the mechanism involved in homogeneous hydrogenation of an olefin by RhCl (pph3)3. c) Write a short note on water-gas shift reaction.

(5+4+3=12)

5. a) Describe the catalytic cycle of hydroformylation reaction of alkenes by HCo (CO)4. b) Discuss the mechanism involved in Fischer-Tropsch process. c) Explain the synthesis of acetic acid by Monsanto process.

(4+4+4 = 12)

*PG317*

-3-

PG – 317

6. a) What is 18 – e rule ? Give its significance. Deduce the total electron count for the following complexes based on both ionic and neutral counting schemes. i) ( η 5 – C5H5) Mo (CO)2 ( η 3 – C3H5) ii) ( η 5 – C5H5)2 ZrCl2 b) Discuss the classification of organometallic compounds based on hapticity of ligands with suitable examples. c) Write the structure of Zeige’s salt and explain the nature of metal-Olefin bond involved. (4+4+4 = 12) 7. a) Describe synthesis, structure and bonding in ferrocene. b) Write a note on structure and bonding in Fischer type carbene complexes. c) What are fluxional molecules ? Explain fluxional behaviour with a suitable example. (5+4+3 = 12)

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