Stereochemistry of imine reduction by a hydroxycyclopentadienyl ruthenium hydride.
The stereochemistry of hydrogen transfer from [2,5-Ph(2)-3,4-Tol(2)(eta(5)-C(4)COD)]Ru(CO)(2)D to N-aryl imines to give amine complexes was shown to be mostly trans stereospecific. Stereospecific hydrogen transfer is proposed to generate an amine and a coordinatively unsaturated ruthenium intermediate in close proximity. Coordination of the amine is proposed to occur faster than lone pair inversion of the amine. In contrast, hydrogen transfer to N-alkyl imines is stereorandom. It is proposed that stereochemistry is lost in part due to the reversibility of the hydrogen transfer being faster than amine coordination.
Casey
Charles P
CP
Department of Chemistry, University of Wisconsin, Madison, WI 53706, USA. casey@chem.wisc.edu
Bikzhanova
Galina A
GA
Guzei
Ilia A
IA
D041961:Deuterium Exchange Measurement; D007097:Imines / Q000737:chemistry*; D009682:Magnetic Resonance Spectroscopy; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000737:chemistry*; D010084:Oxidation-Reduction; D013237:Stereoisomerism; D013816:Thermodynamics
D007097:Imines; D009942:Organometallic Compounds; C506828:hydroxycyclopentadienyl ruthenium hydride