An Isolable Terminal Imido Complex of Palladium and Catalytic Implications
An Isolable Terminal Imido Complex of Palladium and Catalytic Implications
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DOI：
10.1002/anie.201809152
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发表时间：
2018-12-03
影响因子：
16.6
通讯作者：
Munz, Dominik
中科院分区：
文献类型：
--
作者：
Gruenwald, Annette;Orth, Nicole;Munz, Dominik
在这里，我们报道了一个难以捉摸的钯（II）末端亚胺配合物的分离和反应性研究的第一个例子。这种支架被认为是各种催化过程的关键中间体，包括C-H键的胺化。我们通过H-H， C-H， N-H和O-H键证明了亚硝基的易变性，并阐明了它在催化中的作用。高反应活性是由于反键最高已占分子轨道（HOMO）的占据，这导致了封闭壳酰基官能团内独特的电荷分离。因此，Natom转移不一定与金属的高价（Pd-III, Pd-IV）或通常推断的硝基烯的开壳特性有关。
Herein, we report the isolation and a reactivity study of the first example of an elusive palladium(II) terminal imido complex. This scaffold is an alleged key intermediate for various catalytic processes, including the amination of C-H bonds. We demonstrate facile nitrene transfer with H-H, C-H, N-H, and O-H bonds and elucidate its role in catalysis. The high reactivity is due to the population of the antibonding highest occupied molecular orbital (HOMO), which results in unique charge separation within the closed-shell imido functionality. Hence, Natom transfer is not necessarily associated with the high valency of the metal (Pd-III, Pd-IV) or the open-shell character of a nitrene as commonly inferred.