203256-27-3Relevant academic research and scientific papers
Phosphaalkyne hydrometalation: Synthesis and reactivity of the complexes [Ru(P=CHCMe3)Cl(CA)(PPh3)2] (A = O, S)
Bedford, Robin B.,Hill, Anthony F.,Jones, Cameron,White, Andrew J. P.,Williams, David J.,Wilton-Ely, James D. E. T.
, p. 4744 - 4753 (1998)
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.
