Complexes of the platinum metals. Part II. Carboxylato(triphenylphosphine) derivatives of ruthenium, osmium, rhodium, and iridium

Many hydrido- and low oxidation state triphenylphosphine complexes of ruthenium, osmium, rhodium, and iridium are shown to yield carboxylato-derivatives on reaction with carboxylic acids R·CO2H (R = alkyl or aryl) in organic solvents. These reactions provide convenient syntheses for an extensive range of new and previously reported series of carboxylato-complexes including RuH(OCOR)(PPh3)3, RuCl(OCOR)(CO)(PPh3)2, RuH(OCOR)(CO)(PPh3)2 Ru(OCOR)2(CO)(PPh3)2, Ru(OCOR)2(CO)2(PPh3)2, OsH(OCOR)(PPh3)3, Rh(OCOR)(PPh3)3, Rh(OCOR)(CO)(PPh3)2[Rh(Ph2P·CH2·CH2·PPh2)2][OCOR], Rh(OCOR)2(NO)(PPh3)2, IrH2(OCOR)(PPh3)3, and Ir(OCOR)3(PPh3)2. A single-step synthesis of the complexes RuH(OCOR)(PPh3)3 from hydrated ruthenium trichloride is also described. The carboxylato-derivatives are characterised by i.r. and 1H n.m.r. spectroscopy.