COMPLEXES OF THE PLATINUM METALS .46. 1,1,1,5,5,5-HEXAFLUORO-3-AZAPENTANE-2,4-DIIMINATO DERIVATIVES OF RUTHENIUM, OSMIUM AND IRIDIUM - CRYSTAL-STRUCTURE OF [RU(NHC(CF3)NC(CF3)NH)H(CO)(PPH(3))(2)]

Trifluoroacetamidine, NH=C(CF)(3)-NH2, underwent a condensation reaction in the presence of certain platinum metal hydrides in boiling toluene to liberate ammonia and form complexes containing the N.N'-chelating 1,1,1,5,5,5-hexafluoro-3-azapentane-2.4-diiminate ligand NHC(CF3)NC(CF3)NH. Complexes prepared in this manner were [M{NHC(CF3)NC(CF3)NH}H(CO)(PPh(3))(2)], [M(NHC(CF3)NC(CF3)NH}Cl(CO)(PPh(3))(2)], [M{NHC(CF3)NC(CF3)NH}(2)(PPh(3))(2)], (M = Ru or Os) and [Ir(NHC(CF3)NC(CF3)NH}H-2(PPh(3))(2)]. Under similar conditions [Ru(O2CCF3)(2)(CO)(PPh(3))(2)] reacted to afford the complex [Ru{NHC(CF3)NC(CF3)NH}(O2CCF3)(CO)(PPh(3))(2)] in which intramolecular hydrogen bonding between the non-coordinated oxygen of the monodentate trifluoroacetate ligand and the adjacent NH moiety has been detected. An X-ray crystallographic study performed on [Ru{NHC(CF3)NC(CF3)NH}H(CO)(PPh(3))(2)] has confirmed an octahedral ruthenium (II)) structure with trans-phosphine ligands and a chelating NHC(CF3)NC(CF3)NH moiety.