Borane to boryl hydride to borylene dihydride: explicit demonstration of boron-to-metal α-hydride migration in aminoborane activation.

The sequence of fundamental steps implicit in the conversion of a dihydroborane to a metal borylene complex have been elucidated for an [Ir(PMe(3))(3)] system. B-H oxidative addition has been applied for the first time to an aminodihydroborane, H(2)BNR(2), leading to the generation of a rare example of a primary boryl complex, L(n)(H)M{B(H)NR(2)}; subsequent conversion to a borylene dihydride proceeds via a novel B-to-M α-hydride migration. The latter step is unprecedented for group 13 ligand systems, and is remarkable in offering α- substituent migration from a Lewis acidic center as a route to a two-coordinate ligand system