LEWIS-BASE ADDUCTS OF GROUP-11 METAL(I) COMPOUNDS .59. CRYSTAL-STRUCTURE DETERMINATIONS OF TETRAKIS(TRIMETHYLPHOSPHINE)COPPER(I) HALIDES AND TETRAKIS(TRIPHENYLPHOSPHINE)-COPPER(I) AND TETRAKIS(TRIPHENYLPHOSPHINE)-SILVER(I) HEXAFLUOROPHOSPHATES

The crystal structures of [Cu(PMe3)4]X (X = Cl, Br, I) and of [M(PPh3)4] [PF6] (M = Cu, Ag) have been determined by single-crystal X-ray diffraction methods at 295 K. The former compounds contain nearly tetrahedral [Cu(PMe3)4]+ ions on sites of m symmetry with mean Cu-P bond lengths of 2•270, 2•271 and 2•278 A for X = Cl, Br and 1 respectively. The latter compounds contain [M(PPh3)4]+ ions on sites of 3 symmetry. In the M = Ag complex the coordination environment is close to tetrahedral, but in the M = Cu complex the length of the axial Cu-P bond [2-465(2) A] is significantly shorter than that of the off-axis bonds [2•566(2) Å]. Possible reasons for this are discussed. © 1990 ASEG.