Aluminum–Ligand Cooperative N–H Bond Activation and an Example of Dehydrogenative Coupling

Activation of N-H bonds by a molecular aluminum complex via metal-ligand cooperation is described. ((Ph)I2P(2-))AlH (1b), in which (Ph)I2P(2-) is a tridentate bis(imino)pyridine ligand, reacts with anilines to give the N-H-activated products ((Ph)HI2P(-))AlH(NHAr) (2). When heated, 2 releases H2 and affords ((Ph)I2P(-))Al(NHAr) (3). Complex 1b catalyzes the dehydrogenative coupling of benzylamine to afford H2, NH3, and N-(phenylmethylene)benzenemethanamine.