COMPLEXES OF THE PLATINUM METALS .47. PERFLUOROALKYL-AMIDATO AND PERFLUOROARYL-AMIDATO DERIVATIVES OF RUTHENIUM, OSMIUM AND IRIDIUM

Trifluoroacetamide reacted with [RuCl2(PPh(3))(3)]-NEt(3) in boiling t oluene to afford the binuclear species [Ru-2(mu-Cl)(mu-H){mu-NHC(O)CF3 }(2)(PPh(3))(4)] 1a ('head-to-tail' N,O-amidato bridged isomer). In co ntrast use of [RuH(Cl)(PPh(3))(3)] as the ruthenium precursor led to f ormation of la as a mixture of 'head-to-tail' and 'head-to-head' isome rs plus a small; amount of another product 2a which is tentatively for mulated as [Ru-2(mu-H){mu-NHC(O)CF3}(3)(PPh(3))(4)] with one N- and tw o N,O-bridging amidate ligands. Carbonylation of these products; in bo iling toluene yielded dicarbonyl species 2(mu-Cl)(mu-H){mu-NHC(O)CF3}( 2)(CO)(2)(PPh(3))(2)] 3a ('head-to-tail' and 'head-to-head' isomers) p lus a trace of [Ru-2(mu-H){mu-NHC(O)CF3}(3)(CO)(2)(PPh(3))(2)] 4a. Und er similar conditions trifluoroacetamide reacted with [RuH2(CO)(PPh(3) )(3)], [Ru(CO)(3)(PPh(3))(2)], [OsH2(CO)(PPh(3))(3)] and mer-[IrH3(PPh (3))(3)] to yield the mononuclear products [Ru{NHC(O)CF3}(2)(CO)(H2O)( PPh(3))2] 5a, [Ru{NHC(O)CF3}(2)(CO)(2)(PPh(3))(2)] 6a, [OsH{NHC(O)CF3} (CO)(PPh(3))(3)] 7a and [IrH2{NHC(O)CF3}(PPh(3))(3)] 8a respectively, all of which contain monodentate N-bonded trifluoroacetamidate ligands . Pentafluoropropionamide and pentafluorobenzamide yielded analogous p roducts 1b, 2b, 3b and 8b, and 1c respectively. The crystal structure of [Ru-2(mu-Cl)(mu-H){mu-NHC(O)C2F5}(2)(PPh(3))(4)] 1b has been determ ined. All other products were characterised by infrared and NMR spectr oscopy.