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

Abstract

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.