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MCM-41-supported platinum carbonyl cluster-derived catalysts for asymmetric and nonasymmetric hydrogenation reactions

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Title MCM-41-supported platinum carbonyl cluster-derived catalysts for asymmetric and nonasymmetric hydrogenation reactions
 
Creator BASU, SUSMIT
MAPA, MAITRI
GOPINATH, CHINNAKONDA S
DOBLE, MUKESH
BHADURI, SUMIT
LAHIRI, GOUTAM KUMAR
 
Subject x-ray photoelectron spectroscopy
hydrogenation
transmission electron microscopy
reaction kinetics
platinum compounds
 
Description Anionic platinum carbonyl cluster ([Pt12(CO)24]2−) was ion-paired with the 3-chloropropyltrimethoxysilyl-ammonium group chemically bound to the surface of MCM-41. The materials undergo quick decarbonylation and have been characterized before decarbonylation by IR and UV–vis spectroscopy and after decarbonylation by XPS and TEM. They have been used as catalysts for the hydrogenations of methyl pyruvate, acetophenone, nitrobenzene, benzonitrile, and ethylacetoacetate. The support and the quaternary ammonium groups have significant effects on surface platinum concentration, crystallite size, and observed activity. In the hydrogenation of the prochiral substrates methyl pyruvate or acetophenone, the cinchonidine-based catalyst gives significant enantioselectivity under optimum conditions. A kinetic model that includes an enantioselective product-formation step and a hydrogen pressure-dependent step for the deactivation of the enantioselective sites gives reasonable agreement between predicted and observed enantioselectivity. The model is also in accordance with the XPS and TEM data.
 
Publisher Elsevier
 
Date 2009-04-03T09:05:57Z
2011-11-25T20:41:02Z
2011-12-26T13:08:40Z
2011-12-27T05:33:57Z
2009-04-03T09:05:57Z
2011-11-25T20:41:02Z
2011-12-26T13:08:40Z
2011-12-27T05:33:57Z
2006
 
Type Article
 
Identifier Journal of Catalysis 239(1), 154-161
0021-9517
http://dx.doi.org/10.1016/j.jcat.2006.01.032
http://hdl.handle.net/10054/1130
http://dspace.library.iitb.ac.in/xmlui/handle/10054/1130
 
Language en