Transition-metal complexes containing phosphorus ligands. Part XI. Cationic trialkyl phosphite derivatives of gold, silver and the platinum metals

Ligand exchange reactions performed in polar solvents afford a convenient general route to an extensive series of cationic trimethyl and triethul phosphite derivatives of gold, silver and the platinum metals, which were islated as theri tetraphenylborate salts. The products, which were characterised by elemental analysis, proton n.m.r. spectroscopy and conductivity measurements, contain cations of the general formulae {M[P(OR)3]6}2+ (M = Ru, Os);{MX[P(OR)3]5}+ (M = Ru, X = H, Cl, Br, M = Os, X = Br);{M[P(OR)3]5}+ (M = Rh, Ir); {M[p(OR)3]4}2+ and{MCl[P(OR)3]3}+ (M = Pd, Pt) and {M[p(OR)3]4}+ (M = Ag, Au) (R = Me or Et throughout). A qualitative description of the coupling patterns observed in the proton n.m.r. spectra of these cations is given, and is interpreted in terms of ligand rearrangement, exchange and dissociation processes.