Free radicals as intermediates in the oxidative addition of alkyl halides to platinum(0)

Abstract

Free radicals are implicated in the oxidative addition of an alkyl halide RX (MeI, CD₃I, EtI, or PhCH₂Br) to Pt(PPh₃)₃, as shown by identifying (e.s.r.) the derived nitroxide Bu^t(R)NO. using Bu^tNO as a spin trap; a non-chain mechanism is proposed, with the formation of [Pt^IX(PPh₃)₂]· as rate limiting.