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(η5-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(η4-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(η4-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.