The Reactivity Patterns of Low-Coordinate Iron−Hydride Complexes

作者：Ying Yu, Azwana R. Sadique, Jeremy M. Smith, T.R. Dugan, Ryan E. Cowley, William W. Brennessel, Christine J. Flaschenriem, Eckhard Bill, Thomas R. Cundari, Patrick L. Holland · 发表于：Journal of the American Chemical Society · 年份：2008 · DOI：10.1021/ja710669w · 被引用次数：193 · 研究领域：Metalloenzymes and iron-sulfur proteins、Organometallic Complex Synthesis and Catalysis、Metal-Catalyzed Oxygenation Mechanisms

We report a survey of the reactivity of the first isolable iron-hydride complexes with a coordination number less than 5. The high-spin iron(II) complexes [(beta-diketiminate)Fe(mu-H)] 2 react rapidly with representative cyanide, isocyanide, alkyne, N 2, alkene, diazene, azide, CO 2, carbodiimide, and Brønsted acid containing substrates. The reaction outcomes fall into three categories: (1) addition of Fe-H across a multiple bond of the substrate, (2) reductive elimination of H 2 to form iron(I) products, and (3) protonation of the hydride to form iron(II) products. The products include imide, isocyanide, vinyl, alkyl, azide, triazenido, benzo[ c]cinnoline, amidinate, formate, and hydroxo complexes. These results expand the range of known bond transformations at iron complexes. Additionally, they give insight into the elementary transformations that may be possible at the iron-molybdenum cofactor of nitrogenases, which may have hydride ligands on high-spin, low-coordinate metal atoms.