|
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
Synthesis, structures and electrochemical properties of nitro- and amino-functionalized diiron azadithiolates as active site models of Fe-only hydrogenases
点击次数：
论文类型：期刊论文
发表时间：2004-09-20
发表刊物：CHEMISTRY-A EUROPEAN JOURNAL
收录刊物：Scopus、SCIE、EI、PubMed
卷号：10
期号：18
页面范围：4474-4479
ISSN号：0947-6539
关键字：bioinorganic chemistry; cluster compounds; diiron azaditholate; iron only hydrogenase; redox chemistry
摘要：Complex [{(mu-SCH(2))(2)N(4-NO(2)C(6)H(4))}Fe(2)(CO)(6)] (4) was prepared by the reaction of the dianionic intermediate [(mu-S)(2)Fe(2)(CO)(6)](2-) and N,N-bis(chloromethyl)-4-nitroaniline as a biomimetic model of the active site of Fe-only hydrogenase. The reduction of 4 by Pd-C/H(2) under a neutral condition afforded complex [{(mu-SCH(2))(2)N(4-NH(2)C(6)H(4))}Fe(2)(CO)(6)] (5) in 67% yield. Both complexes were characterized by IR, (1)H and (13)C NMR spectroscopy and MS spectrometry. The molecular structure of 4, as determined by X-ray analysis, has a butterfly 2Fe2S core and the aryl group on the bridged-N atom slants to the Fe(2) site. Cyclic voltammograms of 4 and 5 were studied to evaluate their redox properties. It was found that complex 4 catalyzed electrochemical proton reduction in the presence of acetic acid. A plausible mechanism of the electrocatalytic proton reduction is discussed.