649760-17-8Relevant academic research and scientific papers
Use of the tetrahydroborate ligand as gate-keeper and protected hydride ligand: Preparation and study of alkyl hydride and acyl hydride complexes of ruthenium(II)
Duckett, Simon B.,Lowe, John P.,Mawby, Roger J.
, p. 2661 - 2670 (2007/10/03)
Complex 3, [Ru(η2-BH4)(CO)(Et)L2] (L = PMe2Ph) can be converted by nucleophiles L′ {a, PMe 2Ph; b, P(OMe)3; c, Me3CNC; d, CO} to alkyl and acyl complexes [Ru(η1-BH4)(CO)(Et)L 2L′] (4a), [Ru(η2-BH4)(COEt)L 2L′] (5a-d), and [Ru(η1-BH4)(COEt) L2L′2] (7d and isomers 7c and 10c). Deprotection can then be achieved under conditions mild enough to allow study of the resulting alkyl hydride complexes [Ru(CO)(Et)HL2L′] (1a, 1b) and acyl hydride complexes [Ru(COEt)HL2L′2] (8c, 8d) prior to elimination of ethane and propanal respectively, with formation of ruthenium(0) complexes [Ru(CO)L2L′2] (6a, 6b, 6d). With Me 3CNC, however, the final product is (depending on the solvent used) [Ru(CNCMe3)2{C(H)NCMe3}(COEt)L2] (9c) or [Ru(CNCMe3)3(COEt)L2]+ (11c). Successive treatment of [Ru(η2-BH4)(CO)HL 2], 2, with ethene and then CO yields propanal, but turning this into a catalytic cycle is hindered by the greater readiness of 5d to yield propanal non-catalytically (reacting with CO) than catalytically (reacting with H 2). The Royal Society of Chemistry 2006.
Nucleophilic attack on η3-allyl and η 2-tetrahydroborate complexes of ruthenium(II)
Chamberlain, Barbara,Duckett, Simon B.,Lowe, John P.,Mawby, Roger J.,Stott, J. Claire
, p. 2603 - 2614 (2007/10/03)
Reaction of [Ru(CO)(η3-C3H 5)Cl(PMe2Ph)2], 1, with CO and Ag+ yielded 2A and 2B, isomers of [Ru(CO)2-(η3-C 3H5)(PMe2Ph)2]+. Treatment of 2B with BH4- gave [Ru(CO)2(CH 2CH2CH2)(PMe2Ph)2], 7, and [Ru(η2-BH4)-(CO)H(PMe2Ph)2], 6, subsequently obtained from [Ru2(CO)2Cl 4(PMe2Ph)4] and NaBH4. Chloride attacked the metal in 2B, yielding [Ru(CO)2(η1-C 3H5)Cl(PMe2Ph)2], 8, which then reformed 1. Lability of the Ru-HB bond trans to hydride allowed nucleophilic access to the metal in 6, with low-temperature formation of [Ru(η 1-BH4)(CO)-H(L)(PMe2Ph)2] (11, 12, 13, L = PMe2Ph, CO, 4-methylpyridine, respectively). On warming with excess L, these gave H3B·L and [Ru(CO)(H) 2L(PMe2Ph)2] (5, 4, 14, respectively). For L = C2H4, low-temperature NMR studies revealed a rapid equilibrium between 6, C2H4 and [Ru(η 1-BH4)(CO)(η2-C2H 4)H(PMe2Ph)2], 16, with slower conversion to [Ru(η2-BH4)(CO)Et(PMe2Ph)2], 17. The Royal Society of Chemistry 2003.
