Silicon and Phosphinomethanides: A Novel Entry to Hypervalent and Low Valent Organosilicon Chemistry

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Abstract

Phosphinomethanides [R2P-C(X)(Y)]- react with R' 2SiC1 via Si-C bond formation tc give (a) R2P-C(X)(Y)(SiR'3), or, depending on the substituents X and Y, via Si-P bond formation, to give the ylides (b) Rt3Si-PR2=C(X)(Y). The latter rearrange to (a), provided that X and Y are not PR2 substituents. With di- or triphosphinomethanides (X,Y=PR2), the ylides are stable and fluctional, which may be rationalized by a pentacoordinate transition state. With R'2SiC12, diphosphinomethanides form hexacoordinate complexes. In certain cases, these complexes may release silylenes RI2Si via a redox reaction with low valency transition metals. Stable Si(I1) compounds with diphosphinomethanides are obtained under reducing conditions. Various skeleton rearrangements are observed starting from R'SiC13, including novel heterocycles and stable silylene-phosphine donor complexes.

Original languageEnglish
Title of host publicationOrganosilicon Chemistry Set
Subtitle of host publicationFrom Molecules to Materials
Publisherwiley
Pages95-102
Number of pages8
ISBN (Electronic)9783527620777
ISBN (Print)9783527323470
DOIs
StatePublished - 10 Jun 2008

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