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

doi:10.1021/om900182z

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

Research output: Contribution to journal › Article › Research › peer-review

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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 language	English
Pages (from-to)	2744-2755
Number of pages	12
Journal	Organometallics
Volume	28
Issue number	9
DOIs	https://doi.org/10.1021/om900182z
Publication status	Published - 11 May 2009
Externally published	Yes

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

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.",

author = "Walker, {Randon H.} and Miller, {Karla A.} and Scott, {Sara L.} and Cygan, {Zuzanna T.} and Bartolin, {Jeffrey M.} and Kampf, {Jeff W.} and Holl, {Mark M.Banaszak}",

year = "2009",

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doi = "10.1021/om900182z",

language = "English",

volume = "28",

pages = "2744--2755",

journal = "Organometallics",

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T1 - Silylene- and germylene-mediated C-H activation

T2 - Reaction with alkanes, ethers, and amines

AU - Walker, Randon H.

AU - Miller, Karla A.

AU - Scott, Sara L.

AU - Cygan, Zuzanna T.

AU - Bartolin, Jeffrey M.

AU - Kampf, Jeff W.

AU - Holl, Mark M.Banaszak

PY - 2009/5/11

Y1 - 2009/5/11

N2 - 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.

AB - 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.

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U2 - 10.1021/om900182z

DO - 10.1021/om900182z

M3 - Article

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SN - 0276-7333

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EP - 2755

JO - Organometallics

JF - Organometallics

IS - 9

ER -

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

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