title: Hydrogen transfer to carbonyls and imines from a hydroxycyclopentadienyl ruthenium hydride: evidence for concerted hydride and proton transfer.
abstract: Reaction of ([2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)CO)](2)H)Ru(2)(CO)(4)(mu-H) (6) with H(2) formed [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COH)Ru(CO)(2)H] (8), the active species in catalytic carbonyl reductions developed by Shvo. Kinetic studies of the reduction of PhCHO by 8 in THF at -10 degrees C showed second-order kinetics with Delta H(double dagger) = 12.0 kcal mol(-1) and Delta S(double dagger) = -28 eu. The rate of reduction was not accelerated by CF(3)CO(2)H, and was not inhibited by CO. Selective deuteration of the RuH and OH positions in 8 gave individual kinetic isotope effects k(RuH)/k(RuD) = 1.5 +/- 0.2 and k(OH)/k(OD) = 2.2 +/- 0.1 for PhCHO reduction at 0 degrees C. Simultaneous deuteration of both positions in 8 gave a combined kinetic isotope effect of k(OHRuH)/k(ODRuD) = 3.6 +/- 0.3. [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COSiEt(3))Ru(CO)(2)H] (12) and NEt(4)(+)[2,5-Ph(2)-3,4-Tol(2)(eta(4)-C(4)CO)Ru(CO)(2)H](-) (13) were unreactive toward PhCHO under conditions where facile PhCHO reduction by 8 occurred. PhCOMe was reduced by 8 30 times slower than PhCHO; MeN=CHPh was reduced by 8 26 times faster than PhCHO. Cyclohexene was reduced to cyclohexane by 8 at 80 degrees C only in the presence of H(2.) Concerted transfer of a proton from OH and hydride from Ru of 8 to carbonyls and imines is proposed.
authors.affiliation: Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA.
authors.forename: C P
authors.initials: CP
authors.lastname: Casey
authors.forename: S W
authors.initials: SW
authors.lastname: Singer
authors.forename: D R
authors.initials: DR
authors.lastname: Powell
authors.forename: R K
authors.initials: RK
authors.lastname: Hayashi
authors.forename: M
authors.initials: M
authors.lastname: Kavana
mesh_terms: D000447:Aldehydes / Q000737:chemistry*; D006859:Hydrogen / Q000737:chemistry*; D007097:Imines / Q000737:chemistry*; D007659:Ketones / Q000737:chemistry*; D007700:Kinetics; D011522:Protons; D017975:Ruthenium Compounds / Q000737:chemistry*
chemical_list: D000447:Aldehydes; D007097:Imines; D007659:Ketones; D011522:Protons; D017975:Ruthenium Compounds; D006859:Hydrogen