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个人信息Personal Information
教授
博士生导师
硕士生导师
主要任职：无
其他任职：精细化工国家重点实验室副主任、大连理工大学-瑞典皇家工学院分子器件联合研究中心主任
性别：男
毕业院校：大连理工大学
学位：博士
所在单位：化工学院
学科：应用化学. 精细化工
办公地点：大连理工大学西部校区化工实验楼E-223
联系方式：0411-84986493
电子邮箱：sunlc@dlut.edu.cn
Catalytic activation of H2 under mild conditions by an [FeFe]-hydrogenase model via an active mu-hydride species.
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论文类型：期刊论文
发表时间：2013-09-18
发表刊物：Journal of the American Chemical Society
收录刊物：PubMed、Scopus、EI
卷号：135
期号：37
页面范围：13688-13691
ISSN号：1520-5126
摘要：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.