Reaction mechanisms : Part (i) Radical and radical ion reactions

Tanko, James M.

doi:10.1039/b617922n

Cited by 3 publications

(3 citation statements)

References 135 publications

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“…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: 84%

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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.

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Section: Acs Paragon Plus Environmentmentioning

confidence: 84%

“…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 Environmentmentioning

confidence: 99%

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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“…18,20,21 Similar substitution reactions were also proposed for germanium-, tin-, and sulfur-centered molecules. 18,25,29 However, although the radical products were identified by ESR, the reaction mechanism, i.e., concerted versus stepwise, was proposed only on the basis of electronic structure calculations of pertinent substitution transition states. Nevertheless, the elucidation of the underlying bimolecular reaction dynamics in the gas phase under single collision conditions in conjunction with elecronic strucutre and quasiclassical trajectory calculations as conducted in the present work provides for the very first time compelling evidence for the radical substitution mechanism via a pentacoordinated silicon atom.…”

Section: The Journal Of Physical Chemistry Lettersmentioning

confidence: 99%

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

Lucas

Thomas

Yang

et al. 2018

J. Phys. Chem. Lett.

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We present a combined experimental and theoretical investigation of the bimolecular gas-phase reaction of the phenyl radical (CH) with silane (SiH) under single collision conditions to investigate the chemical dynamics of forming phenylsilane (CHSiH) via a bimolecular radical substitution mechanism at a tetracoordinated 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 tetracoordinated 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 (SiHCN) and methylsilane (CHSiH) probed in the circumstellar envelope of the carbon star IRC+10216.

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Reaction Mechanisms. Part 1. Radical and Radical Ion Reactions

Tanko

2007

ChemInform

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Reaction mechanisms : Part (i) Radical and radical ion reactions

Cited by 3 publications

References 135 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

Reaction Mechanisms. Part 1. Radical and Radical Ion Reactions

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