Phosphaalkyne hydrometalation: Synthesis and reactivity of the complexes [Ru(P=CHCMe3)Cl(CA)(PPh3)2] (A = O, S)

Robin B. Bedford; Anthony F. Hill; Cameron Jones; Andrew J.P. White; David J. Williams; James D.E.T. Wilton-Ely

doi:10.1021/om980204c

Phosphaalkyne hydrometalation: Synthesis and reactivity of the complexes [Ru(P=CHCMe₃)Cl(CA)(PPh₃)₂] (A = O, S)

Robin B. Bedford, Anthony F. Hill^*, Cameron Jones, Andrew J.P. White, David J. Williams, James D.E.T. Wilton-Ely

^*Corresponding author for this work

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Abstract

The reaction of [RuHCl(CO)(PPh₃)₃] (1a) with P≡CCMe₃ results in the formation of the phosphaalkenyl complex [Ru(P=CHCMe₃)Cl(CO)(PPh₃)₂] (2a). Being coordinatively unsaturated, 2a reacts reversibly with CO to provide [Ru(P=CHCMe₃)Cl(CO)₂(PPh₃)₂] (3) and with isonitriles (CNR) to provide [Ru(P=CHCMe₃)Cl(CNR)(CO)(PPh₃)₂] [R = CMe₃ (4a), C₆H₃Me₂-2,6 (4b)]. With an excess of CNCMe₃, the salt [Ru(P=CHCMe₃)(CNR)₂(CO)(PPh₃)₂]-Cl 5(Cl) is obtained. The anionic bidentate ligand K[H₂B(bta)₂] (bta = benzotriazolyl) reacts with 2a via chloride displacement to provide [Ru(P=CHCMe₃){H₂B(bta)₂}(CO)(PPh ₃)₂] (6) while the facially tridentate macrocycle 1,4,7-trithiacyclononane ([9]aneS₃) provides [Ru-(P=CHCMe₃)(CO)(PPh₃)([9]aneS₃)]Cl 7(Cl). The thiocarbonyl complex [Ru{P=CHCMe₃)-Cl(CS)(PPh₃)₂] (2b), obtained from [RuHCl(CS)(PPh₃)₃] (1b) and P≡CCMe₃, reacts with [Et₂NH₂][S₂CNEt₂] or [9]aneS₃ to provide [Ru(P=CHCMe₃)(S₂CNEt₂)(CS)(PPh ₃)₂] (8) and [Ru(P=CHCMe₃)(CS)(PPh₃)([9]aneS₃)]Cl 9(Cl), respectively. The salt 5(Cl) or the neutral complex 4a react slowly with air (accelerated by base), to provide the λ⁵-phosphaalkenyl-metallacycle [Ru{P(=O)C(CMe₃)C(=O)}(CNCMe₃)₂(PPh ₃)₂] (10). The reactions of 1a with sodium formate or ferrocene carboxylate provides the complexes [Ru(P=CHCMe₃)(O₂CR)-(CO)(PPh₃)₂] (R = H (11a), C₅H₄Fe(η-C₅H₅) (11b)). The X-ray crystal structure of 11a is reported.

Original language	English
Pages (from-to)	4744-4753
Number of pages	10
Journal	Organometallics
Volume	17
Issue number	21
DOIs	https://doi.org/10.1021/om980204c
Publication status	Published - 12 Oct 1998
Externally published	Yes

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@article{69910893deb0422cb2c37de042f82483,

title = "Phosphaalkyne hydrometalation: Synthesis and reactivity of the complexes [Ru(P=CHCMe3)Cl(CA)(PPh3)2] (A = O, S)",

abstract = "The reaction of [RuHCl(CO)(PPh3)3] (1a) with P≡CCMe3 results in the formation of the phosphaalkenyl complex [Ru(P=CHCMe3)Cl(CO)(PPh3)2] (2a). Being coordinatively unsaturated, 2a reacts reversibly with CO to provide [Ru(P=CHCMe3)Cl(CO)2(PPh3)2] (3) and with isonitriles (CNR) to provide [Ru(P=CHCMe3)Cl(CNR)(CO)(PPh3)2] [R = CMe3 (4a), C6H3Me2-2,6 (4b)]. With an excess of CNCMe3, the salt [Ru(P=CHCMe3)(CNR)2(CO)(PPh3)2]-Cl 5(Cl) is obtained. The anionic bidentate ligand K[H2B(bta)2] (bta = benzotriazolyl) reacts with 2a via chloride displacement to provide [Ru(P=CHCMe3)\{H2B(bta)2\}(CO)(PPh 3)2] (6) while the facially tridentate macrocycle 1,4,7-trithiacyclononane ([9]aneS3) provides [Ru-(P=CHCMe3)(CO)(PPh3)([9]aneS3)]Cl 7(Cl). The thiocarbonyl complex [Ru\{P=CHCMe3)-Cl(CS)(PPh3)2] (2b), obtained from [RuHCl(CS)(PPh3)3] (1b) and P≡CCMe3, reacts with [Et2NH2][S2CNEt2] or [9]aneS3 to provide [Ru(P=CHCMe3)(S2CNEt2)(CS)(PPh 3)2] (8) and [Ru(P=CHCMe3)(CS)(PPh3)([9]aneS3)]Cl 9(Cl), respectively. The salt 5(Cl) or the neutral complex 4a react slowly with air (accelerated by base), to provide the λ5-phosphaalkenyl-metallacycle [Ru\{P(=O)C(CMe3)C(=O)\}(CNCMe3)2(PPh 3)2] (10). The reactions of 1a with sodium formate or ferrocene carboxylate provides the complexes [Ru(P=CHCMe3)(O2CR)-(CO)(PPh3)2] (R = H (11a), C5H4Fe(η-C5H5) (11b)). The X-ray crystal structure of 11a is reported.",

keywords = "X-ray structure, Organometallic macrocycle chemistry, Polyazolyl chelate chemistry, Diyne coordination chemistry, Hydrido-vinylidene complex, Building-blocks, Ruthenium(ii) complexes, Thiocarbonyl complexes, Crystal-structure, Terminal alkynes",

author = "Bedford, \{Robin B.\} and Hill, \{Anthony F.\} and Cameron Jones and White, \{Andrew J.P.\} and Williams, \{David J.\} and Wilton-Ely, \{James D.E.T.\}",

year = "1998",

month = oct,

day = "12",

doi = "10.1021/om980204c",

language = "English",

volume = "17",

pages = "4744--4753",

journal = "Organometallics",

issn = "0276-7333",

publisher = "American Chemical Society",

number = "21",

}

TY - JOUR

T1 - Phosphaalkyne hydrometalation

T2 - Synthesis and reactivity of the complexes [Ru(P=CHCMe3)Cl(CA)(PPh3)2] (A = O, S)

AU - Bedford, Robin B.

AU - Hill, Anthony F.

AU - Jones, Cameron

AU - White, Andrew J.P.

AU - Williams, David J.

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

PY - 1998/10/12

Y1 - 1998/10/12

N2 - The reaction of [RuHCl(CO)(PPh3)3] (1a) with P≡CCMe3 results in the formation of the phosphaalkenyl complex [Ru(P=CHCMe3)Cl(CO)(PPh3)2] (2a). Being coordinatively unsaturated, 2a reacts reversibly with CO to provide [Ru(P=CHCMe3)Cl(CO)2(PPh3)2] (3) and with isonitriles (CNR) to provide [Ru(P=CHCMe3)Cl(CNR)(CO)(PPh3)2] [R = CMe3 (4a), C6H3Me2-2,6 (4b)]. With an excess of CNCMe3, the salt [Ru(P=CHCMe3)(CNR)2(CO)(PPh3)2]-Cl 5(Cl) is obtained. The anionic bidentate ligand K[H2B(bta)2] (bta = benzotriazolyl) reacts with 2a via chloride displacement to provide [Ru(P=CHCMe3){H2B(bta)2}(CO)(PPh 3)2] (6) while the facially tridentate macrocycle 1,4,7-trithiacyclononane ([9]aneS3) provides [Ru-(P=CHCMe3)(CO)(PPh3)([9]aneS3)]Cl 7(Cl). The thiocarbonyl complex [Ru{P=CHCMe3)-Cl(CS)(PPh3)2] (2b), obtained from [RuHCl(CS)(PPh3)3] (1b) and P≡CCMe3, reacts with [Et2NH2][S2CNEt2] or [9]aneS3 to provide [Ru(P=CHCMe3)(S2CNEt2)(CS)(PPh 3)2] (8) and [Ru(P=CHCMe3)(CS)(PPh3)([9]aneS3)]Cl 9(Cl), respectively. The salt 5(Cl) or the neutral complex 4a react slowly with air (accelerated by base), to provide the λ5-phosphaalkenyl-metallacycle [Ru{P(=O)C(CMe3)C(=O)}(CNCMe3)2(PPh 3)2] (10). The reactions of 1a with sodium formate or ferrocene carboxylate provides the complexes [Ru(P=CHCMe3)(O2CR)-(CO)(PPh3)2] (R = H (11a), C5H4Fe(η-C5H5) (11b)). The X-ray crystal structure of 11a is reported.

AB - The reaction of [RuHCl(CO)(PPh3)3] (1a) with P≡CCMe3 results in the formation of the phosphaalkenyl complex [Ru(P=CHCMe3)Cl(CO)(PPh3)2] (2a). Being coordinatively unsaturated, 2a reacts reversibly with CO to provide [Ru(P=CHCMe3)Cl(CO)2(PPh3)2] (3) and with isonitriles (CNR) to provide [Ru(P=CHCMe3)Cl(CNR)(CO)(PPh3)2] [R = CMe3 (4a), C6H3Me2-2,6 (4b)]. With an excess of CNCMe3, the salt [Ru(P=CHCMe3)(CNR)2(CO)(PPh3)2]-Cl 5(Cl) is obtained. The anionic bidentate ligand K[H2B(bta)2] (bta = benzotriazolyl) reacts with 2a via chloride displacement to provide [Ru(P=CHCMe3){H2B(bta)2}(CO)(PPh 3)2] (6) while the facially tridentate macrocycle 1,4,7-trithiacyclononane ([9]aneS3) provides [Ru-(P=CHCMe3)(CO)(PPh3)([9]aneS3)]Cl 7(Cl). The thiocarbonyl complex [Ru{P=CHCMe3)-Cl(CS)(PPh3)2] (2b), obtained from [RuHCl(CS)(PPh3)3] (1b) and P≡CCMe3, reacts with [Et2NH2][S2CNEt2] or [9]aneS3 to provide [Ru(P=CHCMe3)(S2CNEt2)(CS)(PPh 3)2] (8) and [Ru(P=CHCMe3)(CS)(PPh3)([9]aneS3)]Cl 9(Cl), respectively. The salt 5(Cl) or the neutral complex 4a react slowly with air (accelerated by base), to provide the λ5-phosphaalkenyl-metallacycle [Ru{P(=O)C(CMe3)C(=O)}(CNCMe3)2(PPh 3)2] (10). The reactions of 1a with sodium formate or ferrocene carboxylate provides the complexes [Ru(P=CHCMe3)(O2CR)-(CO)(PPh3)2] (R = H (11a), C5H4Fe(η-C5H5) (11b)). The X-ray crystal structure of 11a is reported.

KW - X-ray structure

KW - Organometallic macrocycle chemistry

KW - Polyazolyl chelate chemistry

KW - Diyne coordination chemistry

KW - Hydrido-vinylidene complex

KW - Building-blocks

KW - Ruthenium(ii) complexes

KW - Thiocarbonyl complexes

KW - Crystal-structure

KW - Terminal alkynes

UR - https://www.scopus.com/pages/publications/0005329079

U2 - 10.1021/om980204c

DO - 10.1021/om980204c

M3 - Article

SN - 0276-7333

VL - 17

SP - 4744

EP - 4753

JO - Organometallics

JF - Organometallics

IS - 21

ER -

Phosphaalkyne hydrometalation: Synthesis and reactivity of the complexes [Ru(P=CHCMe₃)Cl(CA)(PPh₃)₂] (A = O, S)

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