| Popis: |
The dihydrogen compound trans-[Ru((R)-BINAP)(H)(eta2-H2)((R,R)-dpen)]+ (2', BINAP = 2,2'-bis(diphenylphosphino)-1,1'-binaphthyl, dpen = 1,2-diphenylethylenediamine) is a proposed intermediate in asymmetric ketone hydrogenations. It quickly reacts at -80 degrees C with 1 equiv of the base KOtBu in 2-PrOH-d8/CH2Cl2-d2 under H2 to generate trans-Ru((R)-BINAP)(H)(2-PrO)((R,R)-dpen) (4). The alkoxide 4 does not react with H2 after hours under ambient conditions. Addition of 1 equiv of KOtBu to 4 produces a hydrogen bonded species 10 that reacts readily with H2 at -80 degrees C to generate the dihydride catalytic intermediate trans-[Ru((R)-BINAP)(H)2((R,R)-dpen)] (3'). Addition of 1 equiv of ((CH3)3Si)2NK to the alkoxide 4 produces the amide catalytic intermediate 5. Compound 5 reacts reversibly with H2 to generate 3'. |
