Pentamethylcyclopentadienyl-rhodium and -iridium complexes. Part VII. Mono-, di-, and tri-µ-hydrido-complexes

Abstract

The complexes [M(C5Me5)Cl2]2, [M(C5Me5)X2]n(M = Rh or Ir; X = OCOCH3 or OCOCF3) are catalysts for the hydrogenation of olefins under ambient conditions. Reaction of these complexes with hydrogen has given the novel compounds [{M(C5Me5)}2HCl3], [{M(C5Me5)}2HX2]Y, [{M(C5Me5)}2H2X]Y, and [{Ir(C5Me5)}2H3]Y [X = OCOCH3 or OCOCF3; Y = PF6, H(OCOCF3)2 or H(OCOCH3)2] which contain mono-, di-, and tri-µ-hydrido-ligands. The mono-µ-hydrido-complexes [{M(C5Me5)}2HX2][HX2](M = Rh or Ir; X = OCOCH3) can also be prepared from [M(C5Me5)(OCOCH3)2] and isopropyl alcohol; in air the isopropyl alcohol is catalytically dehydrogenated to acetone. Hydrolysis of [{M(C5Me5)}2HX2]+(M = Rh, X = OCOCH3 or OCOCF3, M = Ir, X = OCOCH3) leads to complexes which it is suggested contain µ-hydrido-µ-hydroxo-bridges [{M(C5Me5)}2H(OH)X].