Thiocarbamoyl Complexes of Ruthenium(II), Rhodium(III), and Iridium(III)
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- 作者：Anthony F. Hill ; Derek A. Tocher ; Andrew J. P. White ; David J. Williams ; and James D. E. T. Wilton-Ely
- 刊名：Organometallics
- 出版年：2005
- 出版时间：October 24, 2005
- 年：2005
- 卷：24
- 期：22
- 页码：5342 - 5355
- 全文大小：318K
- 年卷期：v.24,no.22(October 24, 2005)
- ISSN：1520-6041
文摘
The reaction of [Ru(CO)2(PPh3)3] (1) or [Ru(
2-CS2)(CO)2(PPh3)2] with N,N-dimethylthiocarbamoyl chloride provides [Ru(2-SCNMe2)(CO)2(PPh2)2]Cl (2·Cl), thermolysis of whichyields [Ru(2-SCNMe2)Cl(CO)(PPh2)2] (3). Treatment of 2·Cl with NaBH4 leads to carbonylsubstitution and formation of [RuH(2-SCNMe2)(CO)(PPh3)2] (4), which is readily convertedto an alternative isomer of [RuCl(2-SCNMe2)(CO)(PPh3)2] (5, Cl trans to S) on treatmentwith hydrochloric acid. The reaction of 2·PF6 with Na[S2CNMe2] gives [Ru(2-SCNMe2)(
2-S2CNMe2)(CO)(PPh3)] (6), which is also the product of the reaction of 1 with {Me2NC(S)}2S.[Ru(2-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 chlorideto provide [Rh(2-SCNMe2)Cl2(PPh3)2] (8), while [RhCl(CS)(PPh3)2] provides the metallacycliccomplex [Rh{2-=C(NMe2)SC(=S)}Cl2(PPh3)2] (9). The complexes [IrCl(CA)(PPh3)2] react withMe2NC(=S)Cl to give the salts [Ir(2-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(2-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 COligand to form [Ir(2-SCNMe2){1-C(=O)H}Cl(PPh3)2] (13) or [Ir(2-SCNMe2){1-C(=O)OEt}Cl(PPh3)2] (14), respectively.
2-CS2)(CO)2(PPh3)2] with N,N-dimethylthiocarbamoyl chloride provides [Ru(2-SCNMe2)(CO)2(PPh2)2]Cl (2·Cl), thermolysis of whichyields [Ru(2-SCNMe2)Cl(CO)(PPh2)2] (3). Treatment of 2·Cl with NaBH4 leads to carbonylsubstitution and formation of [RuH(2-SCNMe2)(CO)(PPh3)2] (4), which is readily convertedto an alternative isomer of [RuCl(2-SCNMe2)(CO)(PPh3)2] (5, Cl trans to S) on treatmentwith hydrochloric acid. The reaction of 2·PF6 with Na[S2CNMe2] gives [Ru(2-SCNMe2)(2-S2CNMe2)(CO)(PPh3)] (6), which is also the product of the reaction of 1 with {Me2NC(S)}2S.[Ru(2-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 chlorideto provide [Rh(2-SCNMe2)Cl2(PPh3)2] (8), while [RhCl(CS)(PPh3)2] provides the metallacycliccomplex [Rh{2-=C(NMe2)SC(=S)}Cl2(PPh3)2] (9). The complexes [IrCl(CA)(PPh3)2] react withMe2NC(=S)Cl to give the salts [Ir(2-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(2-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 COligand to form [Ir(2-SCNMe2){1-C(=O)H}Cl(PPh3)2] (13) or [Ir(2-SCNMe2){1-C(=O)OEt}Cl(PPh3)2] (14), respectively.