Theoretical Investigation on the Abstraction Reaction of H with (CH3)3SiH

Theoretical Investigation on the Abstraction Reaction of H with (CH3)3SiH

The abstraction reaction of H with (CH3)3SiH was investigated at the high levels of ab initio molecule orbital theory. The geometries were optimized at the MP2 level with 6-31G(d) basis set, and G2MP2 level was used for the final energy calculations. The theoretical analysis provides the conclusive...

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Veröffentlicht in:Chemical research in Chinese universities 2002, Vol.18 (1), p.47-51
1. Verfasser: ZHANG Qing-zhu WANG Ming-gang WANG Shao-kun ZHANG Miao LIU Chuan-pu GU Yue-shu
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constant
effect
mechanism
Rate
Reaction
state
transition
Tunneling
Variational
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description The abstraction reaction of H with (CH3)3SiH was investigated at the high levels of ab initio molecule orbital theory. The geometries were optimized at the MP2 level with 6-31G(d) basis set, and G2MP2 level was used for the final energy calculations. The theoretical analysis provides the conclusive evidence that the main process is the hydrogen abstraction from the Si-H bond, leading to the formation of H2 and silyl radicals; the hydrogen abstraction from the C-H bond has a higher barrier and is difficult to react. The kinetics was calculated with canonical variational transition-state theory (CVT) over the temperature range 200-1 000 K, and the theoretical rate constants match well with the later experimental values.
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The geometries were optimized at the MP2 level with 6-31G(d) basis set, and G2MP2 level was used for the final energy calculations. The theoretical analysis provides the conclusive evidence that the main process is the hydrogen abstraction from the Si-H bond, leading to the formation of H2 and silyl radicals; the hydrogen abstraction from the C-H bond has a higher barrier and is difficult to react. The kinetics was calculated with canonical variational transition-state theory (CVT) over the temperature range 200-1 000 K, and the theoretical rate constants match well with the later experimental values.</description><identifier>ISSN: 1005-9040</identifier><identifier>EISSN: 2210-3171</identifier><language>eng</language><publisher>Department of Chemistry, Shandong University, Jinan 250100, P. R. 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The geometries were optimized at the MP2 level with 6-31G(d) basis set, and G2MP2 level was used for the final energy calculations. The theoretical analysis provides the conclusive evidence that the main process is the hydrogen abstraction from the Si-H bond, leading to the formation of H2 and silyl radicals; the hydrogen abstraction from the C-H bond has a higher barrier and is difficult to react. The kinetics was calculated with canonical variational transition-state theory (CVT) over the temperature range 200-1 000 K, and the theoretical rate constants match well with the later experimental values.</abstract><pub>Department of Chemistry, Shandong University, Jinan 250100, P. R. China</pub><tpages>5</tpages></addata></record>
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subjects constant
effect
mechanism
Rate
Reaction
state
transition
Tunneling
Variational
title Theoretical Investigation on the Abstraction Reaction of H with (CH3)3SiH
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