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. (^PhI₂P^2–)­AlH (<b>1b</b>), in which ^PhI₂P^2– is a tridentate bis­(imino)­pyridine ligand, reacts with anilines to give the N–H-activated products (^PhHI₂P^–)­AlH­(NHAr) (<b>2</b>). When heated, <b>2</b> releases H₂ and affords (^PhI₂P^–)­Al­(NHAr) (<b>3</b>). Complex <b>1b</b> catalyzes the dehydrogenative coupling of benzylamine to afford H₂, NH₃, and <i>N</i>-(phenylmethylene)­benzenemethanamine