| Abstract
| - The reactions of the hydride complexes [RuHCl(CA)(PPh3)3] (A = O, S) with P⋮CCMe3 provide coordinatively unsaturated phosphaalkenyl complexes [Ru(PCHCMe3)Cl(CA)(PPh3)2], the ligand addition and substitution reactions of which are discussed.
- The reaction of [RuHCl(CO)(PPh3)3] (1a) with P⋮CCMe3 results in the formation of thephosphaalkenyl complex [Ru(PCHCMe3)Cl(CO)(PPh3)2] (2a). Being coordinatively unsaturated, 2a reacts reversibly with CO to provide [Ru(PCHCMe3)Cl(CO)2(PPh3)2] (3) andwith isonitriles (CNR) to provide [Ru(PCHCMe3)Cl(CNR)(CO)(PPh3)2] [R = CMe3 (4a),C6H3Me2-2,6 (4b)]. With an excess of CNCMe3, the salt [Ru(PCHCMe3)(CNR)2(CO)(PPh3)2]Cl 5(Cl) is obtained. The anionic bidentate ligand K[H2B(bta)2] (bta = benzotriazolyl) reactswith 2a via chloride displacement to provide [Ru(PCHCMe3){H2B(bta)2}(CO)(PPh3)2] (6)while the facially tridentate macrocycle 1,4,7-trithiacyclononane ([9]aneS3) provides [Ru(PCHCMe3)(CO)(PPh3)([9]aneS3)]Cl 7(Cl). The thiocarbonyl complex [Ru{PCHCMe3)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(PCHCMe3)(S2CNEt2)(CS)(PPh3)2] (8) and[Ru(PCHCMe3)(CS)(PPh3)([9]aneS3)]Cl 9(Cl), respectively. The salt 5(Cl) or the neutralcomplex 4a react slowly with air (accelerated by base), to provide the λ5-phosphaalkenylmetallacycle [Ru{P(O)C(CMe3)C(O)}(CNCMe3)2(PPh3)2] (10). The reactions of 1a withsodium formate or ferrocene carboxylate provides the complexes [Ru(PCHCMe3)(O2CR)(CO)(PPh3)2] (R = H (11a), C5H4Fe(η-C5H5) (11b)). The X-ray crystal structure of 11a isreported.
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