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

New copper(I) and silver(I) halide-trimethylphosphine adducts have been pre pared 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 P-31 NMR and vibrational spectroscopy. The complex [Ag4Cl4(PMe3)(3)] is a o ne-dimensional polymer of quasi-cubanoid Ag4Cl4 units disposed with their b ody diagonals coincident with the crystallographic 3 axis, and linked by Ag -Cl units between the four-co-ordinate apical atoms of successive Ag4Cl4 un its, isomorphous with its Cu counterpart. The first solid state NMR study o f Cu/Ag PMe3 complexes is reported. The CP MAS P-31 NMR and the far-IR and Raman spectra of the complexes [{CuI(PMe3)(3)] [CuCl(PMe3)(3)] and [{AgX(PM e3)(2)}(2)] (X = Cl or Br) show the structures to be tetrameric cubane, mon omeric pseudo-tetrahedral and dimeric halide-bridged respectively.