Si–H and Si–Si activation at Pt: synthesis and reactivity of neutral and cationic silyl complexes

Abstract

Reactions of [Pt(PEt₃)₃] (1) with the silanes HSiPh₃, HSiPh₂Me and HSi(OEt)₃ led to the products of oxidative addition, cis-[Pt(H)(SiPh₃)(PEt₃)₂] (2), cis-[Pt(H)(SiPh₂Me)(PEt₃)₂] (3), cis-[Pt(H){Si(OEt)₃}(PEt₃)₂] (cis-4) and trans-[Pt(H){Si(OEt)₃}(PEt₃)₂] (trans-4). The complexes cis-4 and trans-4 can also be generated by hydrogenolysis of (EtO)₃SiSi(OEt)₃ in the presence of 1. Furthermore, the silyl compounds cis-4 and trans-4 react with B(C₆F₅)₃ and CH₃CN by hydride abstraction to give the cationic silyl complex trans-[Pt{Si(OEt)₃}(NCCH₃)(PEt₃)₂][HB(C₆F₅)₃] (8). In addition, the reactivity of the complexes cis-4, trans-4 and 8 towards alkenes and CO was studied using NMR experiments.