869902-56-7Relevant academic research and scientific papers
Thiocarbamoyl complexes of ruthenium(II), rhodium(III), and iridium(III)
Hill, Anthony F.,Tocher, Derek A.,White, Andrew J. P.,Williams, David J.,Wilton-Ely, James D. E. T.
, p. 5342 - 5355 (2008/10/09)
The reaction of [Ru(CO)2(PPh3)3] (1) or [Ru(η2-CS2)(CO)2(PPh3) 2] with N,N-dimethylthio-carbamoyl chloride provides [Ru(η2-SCNMe2)(CO)2(PPh2) 2]Cl (2·C1), thermolysis of which yields [Ru(η 2-SCNMe2)Cl(CO)(PPh2)2] (3). Treatment of 2·C1 with NaBH4 leads to carbonyl substitution and formation of [RuH(η2-SCNMe2)(CO)(PPh 3)2] (4), which is readily converted to an alternative isomer of [RuCl(η2-SCNMe2)(CO)(PPh3) 2] (5, Cl trans to S) on treatment with hydrochloric acid. The reaction of 2·PF6 with Na[S2CNMe2] gives [Ru(η2-SCNMe2)(k2-S2CNMe 2)(CO)(PPh3)] (6), which is also the product of the reaction of 1 with {Me2NC(S)}2S. [Ru(η2- SCNMe2)(CNC6H3Me2-2,6)(CO)(PPh 3)2]Cl (7·C1) is isolated from the reaction between [Ru(CNC6H3Me2-2,6)(CO)(PPh3) 3] and Me2NC(S)Cl. [RhCl(CO)(PPh3) 2], [RhCl(PPh3)3], or [Rh-(cod)(PPh 3)2]PF6 (cod = cycloocta-l,5-diene) react with N,N-dimethylthiocarbamoyl chloride to provide [Rh(η2-SCNMe 2)Cl2(PPh3)2] (8), while [RhCl(CS)(PPh3)2] provides the metallacyclic complex [Rh{k2-=C(NMe2)SC(=S)}Cl2(PPh3) 2] (9). The complexes [IrCl(CA)(PPh3)2] react with Me2NC(=S)Cl to give the salts [Ir(η2-SCNMe 2)Cl(CA)(PPh3)2]Cl (A = O 10·C1, S 12·C1). Photolysis of 10·C1 or treatment with dimethylamine provides the neutral complex [Ir(η2-SCNMe2)Cl 2(PPh3)2] (11), which may be obtained directly by reaction of [IrCl(N2)(PPh3)2] with Me 2NC(S)Cl. Treatment of 10·C1 with NaBH4 or NaOEt proceeds via attack at the CO ligand to form [Ir(η2-SCNMe 2){η1-C(=O)H}Cl(PPh3)2] (13) or [Ir(η2-SCNMe2){η1-C(=O)OEt}-Cl(PPh 3)2] (14), respectively.
