HOSPHINO)-1,1-BINAPHTHYL)(H)-(MECN)(THF)(2)](BF4), A CATALYST SYSTEM FOR HYDROSILYLATION OF KETONES AND FOR ISOMERIZATION, INTRAMOLECULAR HYDROSILYLATION, AND HYDROGENATION OF OLEFINS

(R)-2,2'-Bis(diphenylphosphino)-1,1'-binaphthyl ((R)-BINAP) reacted wi th cis-[Ru(MeCN)(2)(COD)(eta(3)-C3H5)](BF4) (COD=cucloocta-1,5-diene) to generate two isomers of MeCN)((R)-BINAP)((1-3-eta):(5,6-eta)-C8H11) ]-(BF4) (1) that reacted with an excess of dihydrogen gas (pressure H- 2 similar to 1 atm, ambient temperature) in THF and methylene chloride (similar to 5:1) to generate [Ru((R)-BINAP)-(H)(MeCN)(THF)(2)](BF4) ( 2). Reactions effected using 2 mol % 2 as catalyst include hydrogenati on of (Z)-methyl alpha-acetamidocinnamate, hydrosilylation of ethyl ac etoacetate by chlorodimethylsilane, tandem, stereoselective isomerizat ion of (rac)-3-buten-2-ol via a partial kinetic resolution (ee of 3-bu ten-20-ol 42% S at 50% conversion) to initially generate (Z)-2-ol, fol lowed by isomerization of the enol to 2-butanone, and competing isomer ization and intramolecular hydrosilylation of dimethyl-(2-propen-1-oxy )silane.