Reactivity of an Acyclic Silylsilylene toward Ethylene: Migratory Insertion into the Si-Si Bond

Daniel Wendel; Wolfgang Eisenreich; Christian Jandl; Alexander Pöthig; Bernhard Rieger

doi:10.1021/acs.organomet.5b00797

Reactivity of an Acyclic Silylsilylene toward Ethylene: Migratory Insertion into the Si-Si Bond

Daniel Wendel
, Wolfgang Eisenreich
, Christian Jandl
, Alexander Pöthig
, Bernhard Rieger

Technical University of Munich

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

33 Scopus citations

Abstract

The reaction of the only known room-temperature-stable, acyclic silylsilylene, Si{NDipp(SiMe₃)}{Si(SiMe₃)₃}, toward ethylene was investigated. A full conversion to the silirane product Si{CH₂-CH₂}{NDipp(SiMe₃)}{Si(SiMe₃)₃} (1) was observed at ambient temperature. However, heating of the benzene solution under an ethylene atmosphere led to an exceptional Si-Si bond insertion to give the modified silirane Si{CH₂-CH₂}{NDipp(SiMe₃)}{CH₂-CH₂-Si(SiMe₃)₃} (2a). With respect to the mechanism, an NMR experiment using C₂D₄ revealed this reaction to proceed via a migratory insertion of the coordinated ethylene of 1 into the Si-Si bond of the ligand framework and subsequent addition of a second ethylene molecule. Moreover, [4+1] cycloaddition with 2,3-dimethyl-1,3-butadiene to give the corresponding silacyclopent-3-ene ring Si{CH₂-CH₃C=CCH₃-CH₂}{NDipp(SiMe₃)}{Si(SiMe₃)₃} (3) is reported. All structures were fully characterized by single-crystal X-ray analysis and ¹H, ¹³C, and ²⁹Si NMR spectroscopy.

Original language	English
Pages (from-to)	1-4
Number of pages	4
Journal	Organometallics
Volume	35
Issue number	1
DOIs	https://doi.org/10.1021/acs.organomet.5b00797
State	Published - 11 Jan 2016

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@article{d107364a60da415aa49b24314a009041,

title = "Reactivity of an Acyclic Silylsilylene toward Ethylene: Migratory Insertion into the Si-Si Bond",

abstract = "The reaction of the only known room-temperature-stable, acyclic silylsilylene, Si\{NDipp(SiMe3)\}\{Si(SiMe3)3\}, toward ethylene was investigated. A full conversion to the silirane product Si\{CH2-CH2\}\{NDipp(SiMe3)\}\{Si(SiMe3)3\} (1) was observed at ambient temperature. However, heating of the benzene solution under an ethylene atmosphere led to an exceptional Si-Si bond insertion to give the modified silirane Si\{CH2-CH2\}\{NDipp(SiMe3)\}\{CH2-CH2-Si(SiMe3)3\} (2a). With respect to the mechanism, an NMR experiment using C2D4 revealed this reaction to proceed via a migratory insertion of the coordinated ethylene of 1 into the Si-Si bond of the ligand framework and subsequent addition of a second ethylene molecule. Moreover, [4+1] cycloaddition with 2,3-dimethyl-1,3-butadiene to give the corresponding silacyclopent-3-ene ring Si\{CH2-CH3C=CCH3-CH2\}\{NDipp(SiMe3)\}\{Si(SiMe3)3\} (3) is reported. All structures were fully characterized by single-crystal X-ray analysis and 1H, 13C, and 29Si NMR spectroscopy.",

author = "Daniel Wendel and Wolfgang Eisenreich and Christian Jandl and Alexander P{\"o}thig and Bernhard Rieger",

note = "Publisher Copyright: {\textcopyright} 2015 American Chemical Society.",

year = "2016",

month = jan,

day = "11",

doi = "10.1021/acs.organomet.5b00797",

language = "English",

volume = "35",

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T1 - Reactivity of an Acyclic Silylsilylene toward Ethylene

T2 - Migratory Insertion into the Si-Si Bond

AU - Wendel, Daniel

AU - Eisenreich, Wolfgang

AU - Jandl, Christian

AU - Pöthig, Alexander

AU - Rieger, Bernhard

PY - 2016/1/11

Y1 - 2016/1/11

N2 - The reaction of the only known room-temperature-stable, acyclic silylsilylene, Si{NDipp(SiMe3)}{Si(SiMe3)3}, toward ethylene was investigated. A full conversion to the silirane product Si{CH2-CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (1) was observed at ambient temperature. However, heating of the benzene solution under an ethylene atmosphere led to an exceptional Si-Si bond insertion to give the modified silirane Si{CH2-CH2}{NDipp(SiMe3)}{CH2-CH2-Si(SiMe3)3} (2a). With respect to the mechanism, an NMR experiment using C2D4 revealed this reaction to proceed via a migratory insertion of the coordinated ethylene of 1 into the Si-Si bond of the ligand framework and subsequent addition of a second ethylene molecule. Moreover, [4+1] cycloaddition with 2,3-dimethyl-1,3-butadiene to give the corresponding silacyclopent-3-ene ring Si{CH2-CH3C=CCH3-CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (3) is reported. All structures were fully characterized by single-crystal X-ray analysis and 1H, 13C, and 29Si NMR spectroscopy.

AB - The reaction of the only known room-temperature-stable, acyclic silylsilylene, Si{NDipp(SiMe3)}{Si(SiMe3)3}, toward ethylene was investigated. A full conversion to the silirane product Si{CH2-CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (1) was observed at ambient temperature. However, heating of the benzene solution under an ethylene atmosphere led to an exceptional Si-Si bond insertion to give the modified silirane Si{CH2-CH2}{NDipp(SiMe3)}{CH2-CH2-Si(SiMe3)3} (2a). With respect to the mechanism, an NMR experiment using C2D4 revealed this reaction to proceed via a migratory insertion of the coordinated ethylene of 1 into the Si-Si bond of the ligand framework and subsequent addition of a second ethylene molecule. Moreover, [4+1] cycloaddition with 2,3-dimethyl-1,3-butadiene to give the corresponding silacyclopent-3-ene ring Si{CH2-CH3C=CCH3-CH2}{NDipp(SiMe3)}{Si(SiMe3)3} (3) is reported. All structures were fully characterized by single-crystal X-ray analysis and 1H, 13C, and 29Si NMR spectroscopy.

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U2 - 10.1021/acs.organomet.5b00797

DO - 10.1021/acs.organomet.5b00797

M3 - Article

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VL - 35

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ER -

Reactivity of an Acyclic Silylsilylene toward Ethylene: Migratory Insertion into the Si-Si Bond

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