Catalytic Activation of H2 under Mild Conditions by an [FeFe]-Hydrogenase Model via an Active 渭-Hydride Species
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- 作者：Ning Wang ; Mei Wang ; Ying Wang ; Dehua Zheng ; Hongxian Han ; M氓rten S. G. Ahlquist ; Licheng Sun
- 刊名：Journal of the American Chemical Society
- 出版年：2013
- 出版时间：September 18, 2013
- 年：2013
- 卷：135
- 期：37
- 页码：13688-13691
- 全文大小：272K
- 年卷期：v.135,no.37(September 18, 2013)
- ISSN：1520-5126
文摘
A [FeFe]-hydrogenase model (1) containing a chelating diphosphine ligand with a pendant amine was readily oxidized by Fc+ (Fc = Cp2Fe) to a FeIIFeI complex ([1]+), which was isolated at room temperature. The structure of [1]+ with a semibridging CO and a vacant apical site was determined by X-ray crystallography. Complex [1]+ catalytically activates H2 at 1 atm at 25 掳C in the presence of excess Fc+ and P(o-tol)3. More interestingly, the catalytic activity of [1]+ for H2 oxidation remains unchanged in the presence of ca. 2% CO. A computational study of the reaction mechanism showed that the most favorable activation free energy involves a rotation of the bridging CO to an apical position followed by activation of H2 with the help of the internal amine to give a bridging hydride intermediate.