Direct ESR evidence for SH2 type reaction of methyl radical with methylsilane and methylgermane in a low temperature solid: A deuterium labeling study

Komaguchi, Kenji; Norberg, Daniel; Nakazawa, Naoki; Shiotani, Masaru; Persson, Petter; Lunell, Sten

doi:10.1016/j.cplett.2005.04.091

Cited by 8 publications

(32 citation statements)

References 13 publications

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“…the reaction H + Si2H6 → SiH4 + SiH3 is competitive with hydrogen abstraction 18,[20][21] ; similar substitution reactions were also proposed for germanium-, tin-, and sulfur-centered molecules. 18,25,29 Page 9 of 20…”

Section: Acs Paragon Plus Environmentsupporting

confidence: 54%

“…Later, Kulicke et al proposed that in the liquid phase, silanes may undergo substitution reactions via carbon-silicon bond formation, which compete effectively with hydrogen abstraction. 20 Condensed-phase kinetics 18,[20][21] and computational studies [22][23][24][25][26][27][28] with silanes suggest that monosilane (SiH4) is unreactive toward substitution reactions with alkyl radicals, however, that substitution reactions with disilane might be feasible, i.e. the reaction H + Si2H6 → SiH4 + SiH3 is competitive with hydrogen abstraction 18,[20][21] ; similar substitution reactions were also proposed for germanium-, tin-, and sulfur-centered molecules.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 87%

“…This marks the phenylsilane system as a benchmark of a radical substitution mechanism involving carbonsilicon bond formation via a concerted, one step mechanism to unravel the chemical dynamics along with the differential cross sections of polyatomic systems incorporating a heavy silicon atom to eventually define our quantitative understanding of molecular structure, reactivity and at 77 K in the condensed phase, where D3-methyl radicals (CD3·) were replaced by a methyl group (CH3·) in D3-methylsilane (CH3SiD3). 18 Under thermal conditions, this mechanism is problematic with electronic structure calculations revealing a transition state to reaction with a barrier height of 95 kJ mol -1 , 19 which cannot be overcome at 77 K. However, the methyl radical was generated via photolysis of methyl iodide (CH3I) that might lead to reaction via vibrationally excited methyl radicals. Later, Kulicke et al proposed that in the liquid phase, silanes may undergo substitution reactions via carbon-silicon bond formation, which compete effectively with hydrogen abstraction.…”

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

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Bimolecular Reaction Dynamics in the Phenyl - Silane System: Exploring the Prototype of a Radical Substitution Mechanism

Lucas¹,

Thomas²,

Yang³

et al. 2018

Preprint

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We present a combined experimental and theoretical investigation of the bimolecular gas phase reaction of the phenyl radical (C6H5) with silane (SiH4) under single collision conditions to investigate the chemical dynamics of forming phenylsilane (C6H5SiH3) via a bimolecular radical substitution mechanism at a tetra-coordinated silicon atom. Verified by electronic structure and quasiclassical trajectory calculations, the replacement of a single carbon atom in methane by silicon lowers the barrier to substitution thus defying conventional wisdom that tetra-coordinated hydrides undergo preferentially hydrogen abstraction. This reaction mechanism provides fundamental insights into the hitherto unexplored gas phase chemical dynamics of radical substitution reactions of mononuclear main group hydrides under single collision conditions and highlights the distinct reactivity of silicon compared to its isovalent carbon. This mechanism might be also involved in the synthesis of cyanosilane (SiH3CN) and methylsilane (CH3SiH3) probed in the circumstellar envelope of the carbon star IRC+10216. TOC image

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Section: Acs Paragon Plus Environmentsupporting

confidence: 54%

Section: Acs Paragon Plus Environmentmentioning

confidence: 87%

Section: Acs Paragon Plus Environmentmentioning

confidence: 99%

See 1 more Smart Citation

Bimolecular Reaction Dynamics in the Phenyl - Silane System: Exploring the Prototype of a Radical Substitution Mechanism

Lucas¹,

Thomas²,

Yang³

et al. 2018

Preprint

View full text Add to dashboard Cite

show abstract

Section: Acs Paragon Plus Environmentsupporting

confidence: 54%

Section: Acs Paragon Plus Environmentmentioning

confidence: 87%

Bimolecular Reaction Dynamics in the Phenyl - Silane System: Exploring the Prototype of a Radical Substitution Mechanism

Lucas¹,

Thomas²,

Yang³

et al. 2018

Preprint

View full text Add to dashboard Cite

We present a combined experimental and theoretical investigation of the bimolecular gas phase reaction of the phenyl radical (C6H5) with silane (SiH4) under single collision conditions to investigate the chemical dynamics of forming phenylsilane (C6H5SiH3) via a bimolecular radical substitution mechanism at a tetra-coordinated silicon atom. Verified by electronic structure and quasiclassical trajectory calculations, the replacement of a single carbon atom in methane by silicon lowers the barrier to substitution thus defying conventional wisdom that tetra-coordinated hydrides undergo preferentially hydrogen abstraction. This reaction mechanism provides fundamental insights into the hitherto unexplored gas phase chemical dynamics of radical substitution reactions of mononuclear main group hydrides under single collision conditions and highlights the distinct reactivity of silicon compared to its isovalent carbon. This mechanism might be also involved in the synthesis of cyanosilane (SiH3CN) and methylsilane (CH3SiH3) probed in the circumstellar envelope of the carbon star IRC+10216.

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Germanimum: Organometallic Chemistry

Holl¹,

Peck²

2005

Encyclopedia of Inorganic Chemistry

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This article provides an overview of germanium organometallic chemistry from 1994 to 2007. Major advances in the formation and breaking of GeC bonds are discussed as are advances in the physical characterization of these compounds. Recent advances in the formation of organogermanium species containing multiple bonds to germanium and the formation of germanium‐centered radicals and cations are delineated. Applications to the synthesis of germanium‐containing polymers are overviewed.

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Direct ESR evidence for SH2 type reaction of methyl radical with methylsilane and methylgermane in a low temperature solid: A deuterium labeling study

Cited by 8 publications

References 13 publications

Bimolecular Reaction Dynamics in the Phenyl - Silane System: Exploring the Prototype of a Radical Substitution Mechanism

Bimolecular Reaction Dynamics in the Phenyl - Silane System: Exploring the Prototype of a Radical Substitution Mechanism

Bimolecular Reaction Dynamics in the Phenyl - Silane System: Exploring the Prototype of a Radical Substitution Mechanism

Germanimum: Organometallic Chemistry

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