Pyridonate-Supported Titanium(III). Benzylamine as an Easy-To-Use Reductant

The reaction of bis(3-pheny1-2-pyridonate)Ti(NMe2)(2) with excess benzylamine leads to an unexpected reduction of the metal center from Ti(IV) to The reduced titanium species was isolated and revealed as tris(3pheny1-2-pyridonate)Ti(NH2Bn)(2). Ammonia and N-benzyl-1-phenylmethanimine are released as byproducts of the reaction, thereby confirming benzylamine as a mild reductant. This new pyridonate-supported titanium(III) complex has been fully characterized, and experimental data and theoretical calculations confirm a d(1) metal center with no ligand-based radical character. This Ti(III) complex does not react with aminoalkenes, suggesting that radical species are not viable intermediates for the hydroaminoalkylation or hydroamination reaction.