State Key Laboratory of Fine Chemicals, DUT-KTH Joint Education and Research Center on Molecular Devices, Dalian University of Technology (DUT), Dalian 116024, China.
J Am Chem Soc. 2013 Sep 18;135(37):13688-91. doi: 10.1021/ja408376t. Epub 2013 Sep 6.
A [FeFe]-hydrogenase model (1) containing a chelating diphosphine ligand with a pendant amine was readily oxidized by Fc(+) (Fc = Cp2Fe) to a Fe(II)Fe(I) 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 °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.
一种[FeFe]-氢化酶模型（1），其中含有一个螯合双膦配体，带有一个悬垂的胺基，很容易被 Fc(+)（Fc = Cp2Fe）氧化为 Fe(II)Fe(I) 配合物(1)，1在室温下被分离出来。通过 X 射线晶体学确定了1的结构，其中含有一个半桥连的 CO 和一个空缺的顶端位置。在过量 Fc(+)和 P(o-tol)3 的存在下，配合物1在 25°C 下于 1 atm 下催化 H2 的活化。更有趣的是，1在存在约 2%CO 的情况下，其 H2 氧化的催化活性保持不变。反应机理的计算研究表明，最有利的活化自由能涉及桥连 CO 旋转到顶端位置，然后在内部胺的帮助下激活 H2，生成桥连氢化物中间体。
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