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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
Diiron dithiolate complexes containing intra-ligand NH center dot center dot center dot S hydrogen bonds: [FeFe] hydrogenase active site models for the electrochemical proton reduction of HOAc with low overpotential
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论文类型：期刊论文
发表时间：2008-05-14
发表刊物：DALTON TRANSACTIONS
收录刊物：EI、PubMed、SCIE
卷号：18
期号：18
页面范围：2400-2406
ISSN号：1477-9226
摘要：Four diiron dithiolate complexes containing ortho- acylamino- functionalized arenethiolato ligands, [(mu-S-2-RCONHC(6)H(4))(2)Fe(2)(CO)(6)] (R=CH(3), 1; CF(3), 2; C(6)H(5), 3; 4-FC(6)H(4), 4), were synthesized and well characterized as biomimetic models of the Fe-Fe hydrogenase active site. The molecular structures of 3 and 4 were determined by X-ray crystallography. The intra-ligand NH center dot center dot center dot S hydrogen bonds were studied by the X-ray analysis and by the (1)H NMR spectroscopy. The contribution of the NH center dot center dot center dot S hydrogen bonds to the reduction potentials of complexes 1-4 was investigated by electrochemistry. The first reduction potentials of complexes 1-4 exhibit large positive shifts, that is, 220-320 mV in comparison to that of the analogous complex [(mu- SPh)(2)Fe(2)(CO)(6)] and 370-470 mV to that of [(mu- pdt)(2)Fe(2)(CO)(6)] (pdt = propane-1,3-dithiolato). Complex 4 is capable of electrocatalysing proton reduction of acetic acid at relatively low overpotential ( ca. 0.2 V) in acetonitrile.