Stable, but still reactive – investigations on the effects of Lewis acid binding on copper nitrene intermediates,Zeitschrift für anorganische und allgemeine Chemie

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Stable, but still reactive – investigations on the effects of Lewis acid binding on copper nitrene intermediates
Zeitschrift für anorganische und allgemeine Chemie ( IF 1.1 ) Pub Date : 2021-05-16 , DOI: 10.1002/zaac.202100092
Kallol Ray ₁ , Katrin Warm ₂ , Inés Monte Pérez ₂ , Uwe Kuhlmann ₃ , Peter Hildebrandt ₃ , Erik Farquhar ₄ , Marcel Swart ₅

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Copper nitrenes are proposed as reactive intermediates in a number of copper mediated aziridination and amination reactions. However, the isolation and characterization of such intermediates have proved challenging because of their transient nature. One successful approach for the stabilization of the copper-nitrene cores is the employment of a redox innocent Lewis acid (LA) like Sc³⁺. We herein report the stabilization of two transient copper nitrene species 3 and 4 in the absence of LAs by employing electronegative −CF₃ and −NO₂ groups in the nitrene substituent. Detailed investigations of the spectroscopic properties of 3 and 4 by theoretical and experimental methods, and a comparison of their reactivities in presence and absence of LAs provide some vital insights into the effect of LAs on the geometric and electronic structures of the copper nitrenes.

中文翻译：

稳定，但仍具有反应性——路易斯酸结合对氮烯铜中间体的影响的研究

铜氮烯被提议作为许多铜介导的氮丙啶化和胺化反应的反应中间体。然而，这些中间体的分离和表征由于其瞬态性质而被证明具有挑战性。稳定铜-氮烯核的一种成功方法是使用氧化还原无害路易斯酸 (LA)，如 Sc ³⁺。我们在此报告了在没有 LA 的情况下通过在氮烯取代基中使用带负电的 -CF ₃和 -NO ₂基团来稳定两种瞬态铜氮烯物质3和4。3和4的光谱特性的详细研究通过理论和实验方法，以及在存在和不存在 LA 时它们的反应性的比较，为了解 LA 对铜氮烯的几何和电子结构的影响提供了一些重要的见解。

更新日期：2021-07-14

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