Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis.,Nature Communications

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Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis.
Nature Communications ( IF 14.7 ) Pub Date : 2015-Dec-11 , DOI: 10.1038/ncomms10093
Julian G West ₁ , David Huang ₁ , Erik J Sorensen ₁

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The dehydrogenation of unactivated alkanes is an important transformation both in industrial and biological systems. Recent efforts towards this reaction have revolved around high temperature, organometallic C-H activation by noble metal catalysts that produce alkenes and hydrogen gas as the sole products. Conversely, natural desaturase systems proceed through stepwise hydrogen atom transfer at physiological temperature; however, these transformations require a terminal oxidant. Here we show combining tetra-n-butylammonium decatungstate (TBADT) and cobaloxime pyridine chloride (COPC) can catalytically dehydrogenate unactivated alkanes and alcohols under near-UV irradiation at room temperature with hydrogen as the sole by-product. This noble metal-free process follows a nature-inspired pathway of high- and low-energy hydrogen atom abstractions. The hydrogen evolution ability of cobaloximes is leveraged to render the system catalytic, with cooperative turnover numbers up to 48 and yields up to 83%. Our results demonstrate how cooperative base metal catalysis can achieve transformations previously restricted to precious metal catalysts.

中文翻译：

通过协同贱金属催化进行小分子无受体脱氢。

未活化烷烃的脱氢是工业和生物系统中的重要转变。最近对该反应的研究主要围绕贵金属催化剂的高温有机金属 CH 活化，产生烯烃和氢气作为唯一产物。相反，天然去饱和酶系统在生理温度下通过逐步氢原子转移进行；然而，这些转化需要末端氧化剂。在这里，我们展示了四正丁基十钨酸铵（TBADT）和氯化钴肟吡啶（COPC）的结合可以在室温下近紫外照射下催化未活化的烷烃和醇脱氢，氢气作为唯一的副产物。这种不含贵金属的工艺遵循受自然启发的高能和低能氢原子提取途径。利用钴肟的析氢能力使体系具有催化作用，合作转化数高达48，收率高达83%。我们的结果证明了协同贱金属催化如何实现以前仅限于贵金属催化剂的转化。

更新日期：2015-12-14

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