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

详细信息    查看全文

• 作者：Eugene Chong ; Wei Xue ; Tim Storr ; Pierre Kennepohl ; Laurel L. Schafer
• 刊名：Organometallics
• 出版年：2015
• 出版时间：October 26, 2015
• 年：2015
• 卷：34
• 期：20
• 页码：4941-4945
• 全文大小：339K
• ISSN：1520-6041

文摘

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.