The direct double dehydrogenation from primary amines to nitriles without an oxidant or hydrogen acceptor is both intriguing and challenging. In this paper, we describe a non-noble metal catalyst capable of realizing such a transformation with high efficiency. A cobalt-centered N,N-bidentate complex was designed and employed as a metal–ligand cooperative dehydrogenation catalyst. Detailed kinetic studies, control experiments, and DFT calculations revealed the crucial hydride transfer, proton transfer, and hydrogen evolution processes. Finally, a tandem outer-sphere/inner-sphere mechanism was proposed for the dehydrogenation of amines to nitriles through an imine intermediate.

中文翻译：

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钴催化伯胺无受体脱氢生成腈

在没有氧化剂或氢受体的情况下，从伯胺到腈的直接双脱氢既有趣又具有挑战性。在本文中，我们描述了一种能够高效实现这种转化的非贵金属催化剂。设计了一种以钴为中心的N , N-二齿配合物，并将其用作金属-配体协同脱氢催化剂。详细的动力学研究、控制实验和 DFT 计算揭示了关键的氢化物转移、质子转移和析氢过程。最后，提出了一种串联的外球/内球机制，用于通过亚胺中间体将胺脱氢为腈。