Silylene- and germylene-mediated C-H activation: Reaction with alkanes, ethers, and amines

Randon H. Walker, Karla A. Miller, Sara L. Scott, Zuzanna T. Cygan, Jeffrey M. Bartolin, Jeff W. Kampf, Mark M.Banaszak Holl

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29 Citations (Scopus)

Abstract

The reaction of silylene Si[N2( t Bu) 2 C 2 H 2 ] and Ph-X (X = I, Br) in alkane and ethereal solvents results in the formation of C-H activation product [C 2 H 2 ( t Bu 2 )N 2 ]SiRI and an equivalent of benzene or oxidativeaddition product [C 2 H 2 ( t Bu 2 )N 2 ]SiPhI. The ratio of products obtained is dependent upon substrate and concentration. This class of reaction has been extended for Si[N 2 ( t Bu) 2 C 2 H 2 ] and Ge[CH(SiMe 3 ) 2 ] 2 to alkylamines. The primary kinetic isotope effect has been measured for the reaction of Si[N 2 ( t Bu) 2 C 2 H 2 ] with Et 2 O and determined to be k H /k D = 5.1 ± 0.1. The reaction of Ge[CH(SiMe 3 ) 2 ] 2 and Ph-Br with THF was determined to be second order. A large isotope effect ranging from 1.8 to 1.1 was measured for a variety of deuterated aryl halides, consistent with an initial electron transfer to the aryl halide.

Original languageEnglish
Pages (from-to)2744-2755
Number of pages12
JournalOrganometallics
Volume28
Issue number9
DOIs
Publication statusPublished - 11 May 2009
Externally publishedYes

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