Synthesis, Characterization, and Nitrogenase-Relevant Reactions of an Iron Sulfide Complex with a Bridging Hydride

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• 作者：Nicholas A. Arnet ; Thomas R. Dugan ; Fabian S. Menges ; Brandon Q. Mercado ; William W. Brennessel ; Eckhard Bill ; Mark A. Johnson ; Patrick L. Holland
• 刊名：Journal of the American Chemical Society
• 出版年：2015
• 出版时间：October 21, 2015
• 年：2015
• 卷：137
• 期：41
• 页码：13220-13223
• 全文大小：334K
• ISSN：1520-5126

文摘

The FeMoco of nitrogenase is an iron鈥搒ulfur cluster with exceptional bond-reducing abilities. ENDOR studies have suggested that E₄, the state that binds and reduces N₂, contains bridging hydrides as part of the active-site iron-sulfide cluster. However, there are no examples of any isolable iron-sulfide cluster with a hydride, which would test the feasibility of such a species. Here, we describe a diiron sulfide hydride complex that is prepared using a mild method involving C鈥揝 cleavage of added thiolate. Its reactions with nitrogenase substrates show that the hydride can act as a base or nucleophile and that reduction can cause the iron atoms to bind N₂. These results add experimental support to hydride-based pathways for nitrogenase.