Abstract
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.
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