868630-35-7Relevant academic research and scientific papers
Pendant-bridging-chelating-cleavage: A series of bonding modes in ruthenium(II)-BINAPO complexes
Geldbach, Tilmann J.,Chaplin, Adrian B.,Haenni, Kevin D.,Scopelliti, Rosario,Dyson, Paul J.
, p. 4974 - 4980 (2008/10/09)
Reaction of 1,1'-bis(diphenylphosphino)binaphthol (BINAPO, 1) with [RuCl2(η6-arene)]2 in methanol leads to dinuclear BINAPO-bridged Ru compounds [{RuCl2(η6-p- cymene)}2-(μ-BINAPO)], 2a, in near quantitative yield. In dichloromethane or acetonitrile, 1 preferably affords mononuclear species in which one of the phosphine centers remains uncoordinated. These complexes can be further stabilized by reaction with BH3 to afford, for example, [RuCl2(η6-p-cymene)(η1-BINAPO-BH 3)], 4a. Upon heating a mixture of 1 and [RuCl2- (η6-p-cymene)]2 in DMF, P-O bond cleavage occurs to afford [RuCl(η2-PPh2-BINOL)-(η6-p- cymene)], 5a, bearing an anionic PO-chelating ligand. Ligand 1 acts as an intact chelate when reacted with [Ru2(μ-Cl)3(η 6-p-cymene)2][PF6] to yield [RuCl(η6-p-cymene)(η2-BINAPO)]-[PF6], 7. Reaction of 1 with [RuCp(CH3CN)3] [PF6] in acetonitrile or chloroform affords [{RuCp(CH3CN)2} 2(η-BINAPO)][PF6]2, 8, and [RuCp(CH 3CN)(η2-BINAPO)] [PF6], 9, respectively. The solid-state structures of 1, 2a, 4a, and 7 are reported, that of 2a representing a rare structural example of a molecule with a bridging binaphthyl-type ligand.
