title: Reactions of a stable silylene with halocarbons.
abstract: An unusual product formation is observed for the insertion reaction of the thermally stable silylene Si[(NCH(2)Bu(t))(2)C(6)H(4)-1,2][abbrev. as Si(NN)] into the carbon-halogen bond of alkyl or aryl halides RHal (Hal=Cl, Br). In general, depending on the halogen, the reaction either results in a disilane of type (NN)Si(Hal)-(R)Si(NN) for Hal=Cl or a mixture of disilane and the monosilane (NN)Si(R)(Hal) for Hal=Br. The results are put into context to previously suggested mechanisms. The disilane (NN)Si(Hal)-(R)Si(NN)(Hal=Cl or Br) is thermally labile and mild thermolysis yields the corresponding monosilane (NN)Si(R)(Hal) and silylene 1. Additionally, strong evidence is presented for a radical pathway for the reaction of 1 and RHal.
authors.affiliation: Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, UK BN1 9QJ.
authors.forename: Mahmood
authors.initials: M
authors.lastname: Delawar
authors.forename: Barbara
authors.initials: B
authors.lastname: Gehrhus
authors.forename: Peter B
authors.initials: PB
authors.lastname: Hitchcock