Functional phosphines XV. Ruthenium complexes containing C5H8(PR2)2 and image ligands (R = Me, Ph, OPh; R′ = H, Me): synthesis and application to homogeneous 2 bonds on the lefthand sideCdouble bond; length as m-dashO hydrogenation and transfer hydrogenat

Treatment of [Ru(η4-C8H12){η3-(CH2)2CMe}2] with C2 chiral cyclopentane-1,2-diyl-bis(phosphines) trans -1,2-C5H8(PR2)2 in hexane afforded the chelate complexes [Ru{η3-(CH2)2CMe}2{1,2-C5H8(PR2)2}], where R = Me (2), Ph (3), NC5H10 (4), and OPh (5). The mixed-ligand compounds View the MathML source[RuCl2{1,2-C5H8(PR2)2}(Ph2PCH2CR2′NH2)] [R′ = H: R = Me (6), Ph (7), OPh (8); R′ = Me: R = Ph (9)] were obtained by reactions of the bis(2-methylallyl) precursors 2, 3, and 5 with methanolic HCl in acetone, followed by the addition of the required aminophosphine in DMF. The (P∩P)2- and (P∩N)2-chelated complexes [RuCl2{1,2-C5H8(PMe2)2}2] (1) and [RuCl2(Ph2PCH2CMe2NH2)2] (10) resulted from RuCl3 · 3H2O and 1,2-C5H8(PMe2)2 or Ph2PCH2CMe2NH2 under reducing conditions. The crystal structures of 1, 3, 4, 6, 7, 9, and 10 were determined by single-crystal X-ray diffraction. Complexes 7, 9, and 10, activated by KOBu-t, i-PrOH, were used as catalysts for the transfer hydrogenation of acetophenone with i-PrOH as the hydrogen source. Base modified complex 10 also turned out to be an active catalyst for the direct hydrogenation of the ketone by H2 under pressure.