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. ((I2P2-)-I-Ph)AlH (1b), in which (I2P2-)-I-Ph is a tridentate bis(imino)pyridine ligand, reacts with anilines to give the N-H-activated products ((HI2P-)-H-Ph)AlH-(NHAr) (2). When heated, 2 releases H-2 and affords ((I2P-)-I-Ph)Al(NHAr) (3). Complex 1b catalyzes the dehydrogenative coupling of benzylamine to afford H-2, NH3, and N-(phenylmethylene)benzenemethanamine.