Mechanistic investigations of imine hydrogenation catalyzed by cationic iridium complexes

Complexes IrH2(eta6-C6H6)(PiPr3)]BF4 (1) and IrH2(NCMe)3(PiPr3)]BF4 (2) are catalyst precursors for homogeneous hydrogenation of N-benzylideneaniline under mild conditions. Precursor 1 generates the resting state IrH2{eta5-(C6H5)NHCH2Ph}(PiPr3)]BF4 (3), while 2 gives rise to a mixture of IrH{PhN=CH(C6H4)-kappaN,C}(NCMe)2(PiPr3)]BF4 (4) and IrH{PhN=CH(C6H4)-kappaN,C}(NCMe)(NH2Ph)(PiPr3)]BF4 (5), in which the aniline ligand is derived from hydrolysis of the imine. The less hindered benzophenone imine forms the catalytically inactive, doubly cyclometalated compound Ir{HN=CPh(C6H4)-kappaN,C}2(NH2CHPh2)(PiPr3)]BF4 (6). Hydrogenations with precursor 1 are fast and their reaction profiles are strongly dependent on solvent, concentrations, and temperature. Significant induction periods, minimized by addition of the amine hydrogenation product, are commonly observed. The catalytic rate law (THF) is rate = k1]PhN=CHPh]p(H2). The results of selected stoichiometric reactions of potential catalytic intermediates exclude participation of the cyclometalated compounds IrH{PhN=CH(C6H4)-kappaN,C}(S)2(PiPr3)]BF4 S = acetonitrile (4), D6]acetone (7), D4]methanol (8)] in catalysis. Reactions between resting state 3 and D2 reveal a selective sequence of deuterium incorporation into the complex which is accelerated by the amine product. Hydrogen bonding among the components of the catalytic reaction was examined by MP2 calculations on model compounds. The calculations allow formulation of an ionic, outer-sphere, bifunctional hydrogenation mechanism comprising 1) amine-assisted oxidative addition of H2 to 3, the result of which is equivalent to heterolytic splitting of dihydrogen, 2) replacement of a hydrogen-bonded amine by imine, and 3) simultaneous H delta+/H delta- transfer to the imine substrate from the NH moiety of an arene-coordinated amine ligand and the metal, respectively.