Structural and spectroscopic characterisation of linearly coordinated gold(I) tribenzylphosphane complexes

The 1:1 tribenzylphosphane (PBn3) complexes of gold(I)-[(Bn3P)AuX] (X = Cl and Br) have been synthesised, and their structures were determined by single-crystal X-ray crystallography. The compounds are isomorphous, neutral molecules with linearly coordinated P-Au-X arrays. Each structure contains three independent [(Bn3P)AuX] entities lying on the three threefold axes of space group P3c1. The mean bond lengths are Au-Cl 2.302(8), Au-P 2.227(11) angstrom for the chloride and Au-Br 2.404(10), Au-P 2.229(4) angstrom for the bromide. These contrast with the 1:1 adducts previously reported for copper(I), which take the form [Cu(PBn3)(2)][CuX2]. The 1:2 AuX:PBn3 compounds that have been synthesised are formulated as [Au(PBn3)(2)]X center dot nH(2)O (X = Cl, n = 1 or 2; X = I and BF4, n = 0). Single-crystal X-ray structures show that linearly two-coordinate centrosymmetric [Au(PBn3)(2)](+) arrays are found in [Au(PBn3)(2)]Cl center dot H2O and (Au(PBn3)(2)]BF4 with Au-P bond lengths of 2.2988(7) and 2.3016(7) angstrom for the chloride and 2.2975(7) angstrom for the tetrafluoroborate. v(AuX) bands in the far-IR spectra of [(Bn3P)AuX] are assigned at 320 and 227 cm(-1) for X = Cl and X = Br, respectively. The P-31 CP MAS NMR spectra of [(Bn3P)AuX] (X = Cl, Br) and [Au(PBn3)(2)]X (X = Cl center dot H2O, Cl center dot 2H(2)O, I, BF4) are reported, and the observation of (2)J(PP) coupling in the spectrum of [Au(PBn3)(2)]Cl center dot 2H(2)O is consistent with the presence in this complex of noncentrosymmetric cations in which the two phosphorus atoms are inequivalent