Reduction of imines by hydroxycyclopentadienyl ruthenium hydride: intramolecular trapping evidence for hydride and proton transfer outside the coordination sphere of the metal.
Reduction of imines by [2,5-Ph2-3,4-Tol2(eta(5)-C4COH)]Ru(CO)2H (2) produces kinetically stable ruthenium amine complexes. Reduction of an imine by 2 in the presence of an external amine trap gives only the complex of the newly generated amine. Reaction of 2 with H2N-p-C6H4N=CHPh (11), which contains an intramolecular amine trap, gave a 1:1 mixture of [2,5-Ph2-3,4-Tol2(eta(4)-C4CO)](CO)2RuNH(CH2Ph)(C6H4-p-NH2) (8), formed by coordination of the newly generated amine to the ruthenium center, and [2,5-Ph2-3,4-Tol2(eta(4)-C4CO)](CO)2RuNH2C6H4-p-NHCH2Ph (9), formed by coordination of the amine already present in the substrate. These results require transfer of hydrogen to the imine outside the coordination sphere of the metal to give a coordinatively unsaturated intermediate that can be trapped inside the initial solvent cage. Amine diffusion from the solvent cage must be much slower than coordination to the metal center. Mechanisms requiring prior coordination of the substrate to ruthenium would have led only to 8 and can be eliminated.
Casey
Charles P
CP
Department of Chemistry, University of Wisconsin, Madison, Wisconsin 53706, USA. casey@chem.wisc.edu
Bikzhanova
Galina A
GA
Cui
Qiang
Q
Guzei
Ilia A
IA
D018360:Crystallography, X-Ray; D006860:Hydrogen Bonding; D007097:Imines / Q000737:chemistry*; D007700:Kinetics; D008958:Models, Molecular; D008968:Molecular Conformation; D009942:Organometallic Compounds / Q000138:chemical synthesis / Q000737:chemistry*; D010084:Oxidation-Reduction; D044367:Phase Transition; D011522:Protons; D012428:Ruthenium / Q000737:chemistry*
D007097:Imines; D009942:Organometallic Compounds; D011522:Protons; C506828:hydroxycyclopentadienyl ruthenium hydride; D012428:Ruthenium