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

ROBINSON, SD; SAHAJPAL, A; TOCHER, DA; (1995) COMPLEXES OF THE PLATINUM METALS .47. PERFLUOROALKYL-AMIDATO AND PERFLUOROARYL-AMIDATO DERIVATIVES OF RUTHENIUM, OSMIUM AND IRIDIUM. J CHEM SOC DALTON (21) 3497 - 3502.

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Abstract

Trifluoroacetamide reacted with [RuCl2(PPh(3))(3)]-NEt(3) in boiling toluene 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 contrast use of [RuH(Cl)(PPh(3))(3)] as the ruthenium precursor led to formation of la as a mixture of 'head-to-tail' and 'head-to-head' isomers plus a small; amount of another product 2a which is tentatively formulated as [Ru-2(mu-H){mu-NHC(O)CF3}(3)(PPh(3))(4)] with one N- and two N,O-bridging amidate ligands. Carbonylation of these products; in boiling toluene yielded dicarbonyl species [Ru-2(mu-Cl)(mu-H){mu-NHC(O)CF3}(2)(CO)(2)(PPh(3))(2)] 3a ('head-to-tail' and 'head-to-head' isomers) plus a trace of [Ru-2(mu-H){mu-NHC(O)CF3}(3)(CO)(2)(PPh(3))(2)] 4a. Under 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 products 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 determined. All other products were characterised by infrared and NMR spectroscopy.

Type:Article
Title:COMPLEXES OF THE PLATINUM METALS .47. PERFLUOROALKYL-AMIDATO AND PERFLUOROARYL-AMIDATO DERIVATIVES OF RUTHENIUM, OSMIUM AND IRIDIUM
Keywords:CRYSTAL
UCL classification:UCL > School of BEAMS > Faculty of Maths and Physical Sciences > Chemistry

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