Preparation and Reactions of a Novel Five-Coordinate Ruthenium Complex [RuH(BINAP)2]PF6 and Formation of the First Chiral Molecular Hydrogen Complex [RuH(η2-H2)(BINAP)2]PF6 (BINAP = (R)-Bis(diphenylphosphino)-1,1′-binaphthyl)

Abstract
A five-coordinate ruthenium complex with the chiral bisphosphine, (R)-2,2′-bis(diphenylphosphino)-1,1′-binaphthyl (BINAP), [RuH(BINAP)2]PF6 (1) was prepared. The complex 1 was found to be a mixture of two isomers in solution. The exposure of 1 to hydrogen gas gave a chiral molecular hydrogen complex, trans-[RuH(η2-H2)(BINAP)2]PF6 (2). [RuD(η2-HD)(BINAP)2]+ ion formed by introducing D2 gas into a THF-d8 solution of 1 has a H-D coupling constant J(H,D) = 30 Hz (1:1:1), diagnostic of η2-HD complex.