om050514c_si_002.cif (20.23 kB)

Thiocarbamoyl Complexes of Ruthenium(II), Rhodium(III), and Iridium(III)

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posted on 24.10.2005, 00:00 by Anthony F. Hill, Derek A. Tocher, Andrew J. P. White, David J. Williams, James D. E. T. Wilton-Ely
The reaction of [Ru(CO)2(PPh3)3] (1) or [Ru(η2-CS2)(CO)2(PPh3)2] with N,N-dimethylthiocarbamoyl chloride provides [Ru(η2-SCNMe2)(CO)2(PPh2)2]Cl (2·Cl), thermolysis of which yields [Ru(η2-SCNMe2)Cl(CO)(PPh2)2] (3). Treatment of 2·Cl with NaBH4 leads to carbonyl substitution and formation of [RuH(η2-SCNMe2)(CO)(PPh3)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)(κ2-S2CNMe2)(CO)(PPh3)] (6), which is also the product of the reaction of 1 with {Me2NC(S)}2S. [Ru(η2-SCNMe2)(CNC6H3Me2-2,6)(CO)(PPh3)2]Cl (7·Cl) 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)(PPh3)2]PF6 (cod = cycloocta-1,5-diene) react with N,N-dimethylthiocarbamoyl chloride to provide [Rh(η2-SCNMe2)Cl2(PPh3)2] (8), while [RhCl(CS)(PPh3)2] provides the metallacyclic complex [Rh{κ2-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-SCNMe2)Cl(CA)(PPh3)2]Cl (A = O 10·Cl, S 12·Cl). Photolysis of 10·Cl or treatment with dimethylamine provides the neutral complex [Ir(η2-SCNMe2)Cl2(PPh3)2] (11), which may be obtained directly by reaction of [IrCl(N2)(PPh3)2] with Me2NC(S)Cl. Treatment of 10·Cl with NaBH4 or NaOEt proceeds via attack at the CO ligand to form [Ir(η2-SCNMe2){η1-C(O)H}Cl(PPh3)2] (13) or [Ir(η2-SCNMe2){η1-C(O)OEt}Cl(PPh3)2] (14), respectively.