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The question of C- vs. O-silylation of ketenes: electrophilic triethylsilylation of diphenylketene

Authors :
Prakash, G.K. Surya
Bae, Chulsung
Rasul, Golam
Olah, George A.
Source :
Proceedings of the National Academy of Sciences of the United States. May 3, 2005, Vol. 102 Issue 18, p6251, 4 p.
Publication Year :
2005

Abstract

Electrophilic triethylsilylation of diphenylketene leads to exclusive C-silylation giving the diphenyl(triethylsilyl)acetyl cation in the solution phase even though density functional theory calculations at the B3LYP/6-311+G* level indicate that the O-silylation of diphenylketene is preferred over C-silylation by 5.4 kcal/mol in the gas phase. On the other hand, in the case of the parent ketene, similar density functional theory calculations show that C-silylation is preferred over O-silylation by 8.2 kcal/mol.

Subjects

Subjects :
Science and technology

Details

Language :
English
ISSN :
00278424
Volume :
102
Issue :
18
Database :
Gale General OneFile
Journal :
Proceedings of the National Academy of Sciences of the United States
Publication Type :
Academic Journal
Accession number :
edsgcl.132873590