Structural, vibrational and solid state CP MAS 31P NMR spectroscopic studies of complexes of trimethylphosphine with copper(I) and silver(I) halides

Abstract

New copper(I) and silver(I) halide–trimethylphosphine adducts have been prepared by reaction of MX with PMe₃ in benzene suspension, and characterised by room-temperature single-crystal X-ray studies and/or solid state CP MAS ³¹P NMR and vibrational spectroscopy. The complex [Ag₄Cl₄(PMe₃)₃] is a one-dimensional polymer of quasi-cubanoid Ag₄Cl₄ units disposed with their body diagonals coincident with the crystallographic 3 axis, and linked by Ag–Cl units between the four-co-ordinate apical atoms of successive Ag₄Cl₄ units, isomorphous with its Cu counterpart. The first solid state NMR study of Cu/Ag PMe₃ complexes is reported. The CP MAS ³¹P NMR and the far-IR and Raman spectra of the complexes [{CuI(PMe₃)}₄], [CuCl(PMe₃)₃] and [{AgX(PMe₃)₂}₂] (X = Cl or Br) show the structures to be tetrameric cubane, monomeric pseudo-tetrahedral and dimeric halide-bridged respectively.