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.双(3-苯基-2-吡啶酮合)二(二甲氨基)钛与过量苄胺的反应，会使金属中心从钛(IV)意外还原为钛(III)。该还原态钛物种经分离后被表征为三(3-苯基-2-吡啶酮合)钛(NH2Bn)2。反应副产物为氨与N-苄基-1-苯基甲亚胺，由此证实苄胺是一种温和还原剂。这种新型吡啶酮配位的钛(III)配合物已得到充分表征，实验数据与理论计算均证实其金属中心为d1构型，且无配体自由基特征。该钛(III)配合物不与氨基烯烃发生反应，这表明自由基物种并非氢氨基烷基化反应或氢胺化反应的可行中间体。