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

Anthony F. Hill; Derek A. Tocher; Andrew J.P. White; David J. Williams; James D.E.T. Wilton-Ely

doi:10.1021/om050514c

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

Anthony F. Hill^*, Derek A. Tocher, Andrew J.P. White, David J. Williams, James D.E.T. Wilton-Ely

^*Corresponding author for this work

Research School of Chemistry

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19 Citations (Scopus)

Abstract

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.

Original language	English
Pages (from-to)	5342-5355
Number of pages	14
Journal	Organometallics
Volume	24
Issue number	22
DOIs	https://doi.org/10.1021/om050514c
Publication status	Published - 24 Oct 2005

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10.1021/om050514c

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@article{e11e1255a53c4abc80fe32e650adcc9b,

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

abstract = "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.",

author = "Hill, \{Anthony F.\} and Tocher, \{Derek A.\} and White, \{Andrew J.P.\} and Williams, \{David J.\} and Wilton-Ely, \{James D.E.T.\}",

year = "2005",

month = oct,

day = "24",

doi = "10.1021/om050514c",

language = "English",

volume = "24",

pages = "5342--5355",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "22",

}

TY - JOUR

T1 - Thiocarbamoyl Complexes of Ruthenium(II), Rhodium(III), and Iridium(III)

AU - Hill, Anthony F.

AU - Tocher, Derek A.

AU - White, Andrew J.P.

AU - Williams, David J.

AU - Wilton-Ely, James D.E.T.

PY - 2005/10/24

Y1 - 2005/10/24

N2 - 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.

AB - 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.

UR - https://www.scopus.com/pages/publications/27544474630

U2 - 10.1021/om050514c

DO - 10.1021/om050514c

M3 - Article

SN - 0276-7333

VL - 24

SP - 5342

EP - 5355

JO - Organometallics

JF - Organometallics

IS - 22

ER -

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

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Correction to: Thiocarbamoyl Complexes of Ruthenium(II), Rhodium(III), and Iridium(III) (vol 24, pg 5342, 2005)

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