Alkyl group transfer from rhodium(I) to electrophilic reagents; inducement by a tertiary phosphine

Abstract

Although the compound RhMe(CO){MeC(CH₂PPh₂)₃}(1) is normally inert to methyl iodide, chlorotrimethyltin and acetone, it reacts in the presence of trimethylphosphine with (a) methyl iodide to form the cationic complex [Rh(CO)(PMe₃){MeC(CH₂PPh₂)₃}]⁺(2), methane, and ethylene but not ethane, (b) chlorotrimethyltin to form (2) and tetramethyltin, and (c) acetone to form (2) and t-butoxide; the role of the trimethylphosphine seems to involve substituting one arm of the triphosphine, thus rendering the Rh–Me moiety more reactive towards electrophilic reagents.