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

The reaction of bis­(3-phenyl-2-pyridonate)­Ti­(NMe2)2 with excess benzylamine leads to an unexpected reduction of the metal center from Ti­(IV) to Ti­(III). The reduced titanium species was isolated and revealed as tris­(3-phenyl-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 d1 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.