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Issue 11, 2011
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The initiation mechanisms for surface hydrosilylation with 1-alkenes

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Hydrosilylation provides a route to form substituted silanes in solution. A similar reaction has been observed in the formation of covalent organic monolayers on a hydrogen-terminated silicon surface and is called thermal hydrosilylation. In solution, the mechanism requires a catalyst to add the basal silicon and saturating hydrogen to the C[double bond, length as m-dash]C double bond. On the silicon surface, however, the reaction proceeds efficiently at 200 °C, initiated by visible light, and more slowly at room temperature in the dark. Such low activation energy barriers for the reactions on a surface relative to that required for solution hydrosilylation are remarkable, and although many explanations have been suggested, controversy still exists. In this work using a constrained molecular dynamics approach within the density functional theory framework, we show that the free energy activation barrier for abstraction of a hydrogen from silicon by an alkene molecule can be overcome by visible light or thermal excitation. Furthermore, we show that by concerted transfer of a hydrogen from the α-carbon to the β-carbon, a 1-alkene can insert its α-carbon into a surface Si–H bond to accomplish hydrosilylation.

Graphical abstract: The initiation mechanisms for surface hydrosilylation with 1-alkenes

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Article information

01 Oct 2010
23 Dec 2010
First published
21 Jan 2011

Phys. Chem. Chem. Phys., 2011,13, 4862-4867
Article type

The initiation mechanisms for surface hydrosilylation with 1-alkenes

M. V. Lee, R. Scipioni, M. Boero, P. L. Silvestrelli and K. Ariga, Phys. Chem. Chem. Phys., 2011, 13, 4862
DOI: 10.1039/C0CP01992E

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