Characterization of a Reactive Rh2 Nitrenoid by Crystalline Matrix Isolation,Journal of the American Chemical Society

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Characterization of a Reactive Rh2 Nitrenoid by Crystalline Matrix Isolation
Journal of the American Chemical Society ( IF 14.4 ) Pub Date : 2019-09-24 , DOI: 10.1021/jacs.9b09064
Anuvab Das ₁ , Yu-Sheng Chen ₂ , Joseph H Reibenspies ₁ , David C Powers ₁

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The fleeting lifetimes of reactive intermediates in C-H functionalization chemistry often prevent their direct characterization. For example, the critical nitrenoid intermediates that mediate Rh2-catalyzed C-H amination have eluded characterization for more than 40 years. In the absence of structural characterization of these species, methodological development is often computationally guided. Here we report the first X-ray crystal structure of a reactive Rh2 nitrenoid, enabled by N2 elimination from an organic azide ligand within a single-crystal matrix. The resulting high-resolution structure displays metrical parameters consistent with a triplet nitrene complex of Rh2. The demonstration of facile access to reactive metal nitrenoids within a crystalline matrix provides a platform for structural characterization of the transient species at the heart of C-H functionalization.

中文翻译：

通过结晶基质分离表征反应性 Rh2 硝烯类化合物

CH 官能化化学中反应中间体的短暂寿命通常会阻止它们的直接表征。例如，40 多年来，介导 Rh2 催化 CH 胺化的关键氮烯中间体一直没有得到表征。在缺乏这些物种的结构特征的情况下，方法学开发通常以计算为指导。在这里，我们报告了反应性 Rh2 氮烯化合物的第一个 X 射线晶体结构，通过从单晶基质内的有机叠氮化物配体中消除 N2 实现。由此产生的高分辨率结构显示的度量参数与 Rh2 的三线态氮烯复合物一致。

更新日期：2019-09-24

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