Reactions of O-alkyl and O-cycloalkyl S-methyl xanthates with MCI(PPh3)3(M = Rh, Ir) and M(PPh3)4(M = Pd, Pt). Easy 1,2-bond shifts in alkyl and cycloalkyl–metal intermediates

Abstract

Reactions of O-alkyl and O-cycloalkyl S-methyl xanthates with RhCl(PPh₃)₃(1), IrCl(PPh₃)₃(2), Pd(PPh₃)₄(3), or Pt(PPh₃)₄(4) at temperatures from 373 to 423 K give olefinic products whose structures clearly reveal 1,2-bond shift skeletal rearrangements in alkyl–metal intermediates; these rearrangements are exactly analogous to several of those occurring in hydroisomerisation of cycloalkanes and alkanes at elevated temperatures on transition metal surfaces.