Synthesis of (diphenylphosphinothioyl)methyldiphenylphosphoniomethanide complexes of gold and silver. X-Ray structure of [Au(C6F5){SPh2PCH[Au(C6F5)]PPh2Me}]
Abstract
Both [Au(C6F5)3(SPh2PCHPPh2Me)]{obtained from [Au(C6F5)3(OEt2)] and [SPh2PCH2PPh2Me]ClO4, followed by deprotonation with NaH} and the free methanide SPPh2CHPPh2Me react with gold(I) or silver(I) complexes [Au(C6F5)(tht)](tht = tetrahydrothiophene), [Au(tht)2]ClO4, and [Ag(OClO3)(PPh3)] to afford binuclear complexes of the types [Au(C6F5){SPh2 PCH[Au(C6F5)]PPh2Me}] or [{M(SPh2PCHPPh2Me)}2][ClO4]2(M = Au or Ag). The silver complex can also be obtained by deprotonation of [{Ag(SPh2PCH2PPh2Me)}2][ClO4]2 with Na2CO3. Oxidative addition of chlorine to the gold derivative gives the binuclear gold(II) complex [{AuCl(SPh2PCHPPh2Me)}2]. The structure of [Au(C6F5){SPh2PCH[Au(C6F5)] PPh2Me}] has been established by X-ray crystallography [space group P21/c, with a= 15.392(4), b= 12.643(5), c= 21.965(7)Å, β= 107.95(2)°, and R′= 0.072 for 3 166 unique observed reflections]. The molecule adopts a folded conformation with parallel, eclipsed C6F5 rings and a corresponding short Au ⋯ Au contact of 3.224 Å.