Acceptorless dehydrogenation of small molecules through cooperative base metal catalysis

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 pr...

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Bibliographic Details
Published in:Nature communications 2015-12, Vol.6 (1), p.10093-10093, Article 10093
Main Authors: West, Julian G, Huang, David, Sorensen, Erik J
Format: Article
Language:English
Subjects:
Alkanes - chemistry
Catalysis
Hydrogen - chemistry
Metals - chemistry
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Summary: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.
ISSN:2041-1723
2041-1723
DOI:10.1038/ncomms10093