Staff Publications

Staff Publications

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    'Staff publications' is the digital repository of Wageningen University & Research

    'Staff publications' contains references to publications authored by Wageningen University staff from 1976 onward.

    Publications authored by the staff of the Research Institutes are available from 1995 onwards.

    Full text documents are added when available. The database is updated daily and currently holds about 240,000 items, of which 72,000 in open access.

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Record number 404987
Title Mimicking the silicon surface: reactivity of silyl radical cations toward nucleophiles
Author(s) Rijksen, B.M.G.; Lagen, B. van; Zuilhof, H.
Source Journal of the American Chemical Society 133 (2011)13. - ISSN 0002-7863 - p. 4998 - 5008.
DOI http://dx.doi.org/10.1021/ja110844e
Department(s) Laboratory for Organic Chemistry
VLAG
Publication type Refereed Article in a scientific journal
Publication year 2011
Keyword(s) hydrogen-terminated silicon - organic monolayers - alkyl monolayers - si(111) surfaces - porous silicon - si - functionalization - oligosilanes - attachment - 1-alkenes
Abstract Radical cations of selected low molecular-weight silicon model compounds were obtained by photoinduced electron transfer. These radical cations react readily with a variety of nucleophiles, regularly used in monolayer fabrication onto hydrogen-terminated silicon. From time-resolved kinetics, it was concluded that the reactions proceed via a bimolecular nucleophilic attack to the radical cation. A secondary kinetic isotope effect indicated that the central Si-H bond is not cleaved in the rate-determining step. Apart from substitution products, also hydrosilylation products were identified in the product mixtures. Observation of the substitution products, combined with the kinetic data, point to an bimolecular reaction mechanism involving Si-Si bond cleavage. The products of this nucleophilic substitution can initiate radical chain reactions leading to hydrosilylation products, which can independently also be initiated by dissociation of the radical cations. Application of these data to the attachment of organic monolayers onto hydrogen-terminated Si surfaces via hydrosilylation leads to the conclusion that the delocalized Si radical cation (a surface-localized hole) can initiate the hydrosilylation chain reaction at the Si surface. Comparison to monolayer experiments shows that this reaction only plays a significant role in the initiation, and not in the propagation steps of Si-C bond making monolayer formation
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