Reactivity of coordinated [Ph2PCHP(S)Ph2]- and [Ph2P(S)CHP(S)Ph2]-: two-center, regiospecific reactivity in rhodium and iridium complexes and formation of a disubstituted methylene bridge between platinum atoms

Abstract

Reaction of methyl iodide with [Ir(Ph,P(S)-CHP(S)Ph,](cod)] occurs in a regiospecific sequence to form first [Ir{Ph,P(S)CHMeP(S)Ph,](cod)] I and only subsequently [IrMeI(Ph,P(S)CHMeP(S)Ph,](cod)] I. For [Rh-(Ph,PCHP(S)Ph,](cod)] the addition sequence is reversed. [Pt(Ph,P(S)CHP(S)Ph,)(MeOcod)] shows both ligand and metal site reactivity in transforming a novel dimer, [Pt,{Ph,P(S)CP(S)Ph,)(MeOcod),] , containing a quaternary carbon bridge between two platinum centers. The bridging carbon is part of four-member C,S chelate rings at both platinums.