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Updated: Aug 16, 2026

Isolating Free Carbenes, their Mixed Dimers and Organic Radicals
Published on: April 19, 2019
Reactions of a stable silylene with halocarbons
Mahmood Delawar1, Barbara Gehrhus, Peter B Hitchcock
1Department of Chemistry, School of Life Sciences, University of Sussex, Brighton, UK BN1 9QJ.
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.
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