Metal/Support Interactions Regulate Substrate Binding in Fe/Co/Se Cluster Catalysts
Metal/Support Interactions Regulate Substrate Binding in Fe/Co/Se Cluster Catalysts
复制标题
金属/载体相互作用调节 Fe/Co/Se 簇催化剂中的底物结合
DOI：
10.1021/acs.inorgchem.3c01601
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发表时间：
2023
影响因子：
4.6
通讯作者：
Velian, Alexandra
中科院分区：
文献类型：
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作者：
Mitchell, Benjamin S.;Chirila, Andrei;Zhou, Daniel Y.;Kephart, Jonathan A.;Velian, Alexandra
在这里，我们研究了 Fe/Co6Se8 分子簇家族的立体电子学要求，以实现甲苯磺酰叠氮化物和叔丁基异氰化物催化偶联的底物亲和力的金发姑娘状态。探索了原位观察的具有催化能力的铁氮烯中间体的反应性，以实现氮烯转移和氢原子提取。异氰化物的双重作用暴露出来，一方面，它可以防止催化剂降解，但大量使用时，会减慢反应活性。研究了远端变化（邻近活性位点的数量和支持配体的身份）对底物亲和力、电子特性和催化活性的影响。总体而言，该研究表明，底物 (tBuNC)、活性位点 (Fe) 和支撑物 (Co6Se8) 之间的动态推拉相互作用创造了一种机制，在该机制中，底物活化增加，并易于解离。
Here, we investigate the stereoelectronic requirements of a family of Fe/Co6Se8molecular clusters to achieve a Goldilocks regime of substrate affinity for the catalytic coupling of tosyl azide andtert-butyl isocyanide. The reactivity of a catalytically competent iron-nitrenoid intermediate, observedin situ, is explored toward nitrene transfer and hydrogen-atom abstraction. The dual role of isocyanide, which, on the one hand, prevents catalyst degradation but, in large amounts, slows down reactivity, is exposed. The impact of distal changes (the number of neighboring active sites and the identity of supporting ligands) on the substrate affinity, electronic properties, and catalytic activity is investigated. Overall, the study reveals that the dynamic, push–pull interactions between the substrate (tBuNC), active site (Fe), and support (Co6Se8) create a regime where increased substrate activation occurs with facile dissociation.