title: The question of C- vs. O-silylation of ketenes: electrophilic triethylsilylation of diphenylketene.
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.
authors.affiliation: Loker Hydrocarbon Research Institute and Department of Chemistry, University of Southern California, University Park, Los Angeles, CA 90089-1661, USA.
authors.forename: G K Surya
authors.initials: GK
authors.lastname: Prakash
authors.forename: Chulsung
authors.initials: C
authors.lastname: Bae
authors.forename: Golam
authors.initials: G
authors.lastname: Rasul
authors.forename: George A
authors.initials: GA
authors.lastname: Olah