Cobalt Silylenes as Platforms for Catalytic Nitrene‐Group Transfer by Metal–Ligand Cooperation.
Cobalt Silylenes as Platforms for Catalytic Nitrene‐Group Transfer by Metal–Ligand Cooperation.
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钴硅烯作为金属-配体合作催化氮烯-基团转移的平台。
DOI：
10.1002/anie.202205748
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发表时间：
2022
期刊：
影响因子：
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通讯作者：
Kohen, Daniela
中科院分区：
文献类型：
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作者：
Whited, Matthew T.;Han, Wenlai;Jin‐Lee, Helen J.;DiNardo, Zach;Watson, Emma;Zhang, Jia;Kohen, Daniela
钴硅基 (Co=Si) 连接能够实现有机叠氮化物的独特金属/配体协同活化，其中氮烯在 Co⋅⋅⋅Si 连接之间发生转移，而配体不会从 18 电子钴中心解离。该过程利用硅和钴位点的正交结合亲和力来避免 CO 中毒，否则会抑制反应活性，从而与相关系统相比，显着改善催化异氰酸酯的生成。双位点方法证明了金属/主族键获得新的高效催化途径的潜力。
A cobalt silylene (Co=Si) linkage enables a distinct metal/ligand cooperative activation of an organic azide, where nitrene transfer occurs to and from the Co⋅⋅⋅Si linkage without ligand dissociation from the 18‐electron cobalt center. This process utilizes the orthogonal binding affinities of the silicon and cobalt sites to avoid CO poisoning that would otherwise inhibit reactivity, leading to significantly improved catalytic isocyanate generation compared with related systems. The dual‐site approach demonstrates the potential of metal/main‐group bonds to access new and efficient catalytic pathways.