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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：中国化学会创始会士、常务理事，中国化工学会会士
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. 化学生物学
办公地点：大连理工大学西部校区知顺楼F-202#
http://peng-group.dlut.edu.cn/
联系方式：大连理工大学西部校区知顺楼F-202 辽宁省大连市高新区凌工路2号，大连116024 课题组网址：http://peng-group.dlut.edu.cn/ E-mail: pengxj@dlut.edu.cn
电子邮箱：pengxj@dlut.edu.cn
Tris(N-pyrrolidinyl)phosphine substituted diiron dithiolate related to iron-only hydrogenase active site: Synthesis, characterization and electrochemical properties
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论文类型：期刊论文
发表时间：2006-11-01
发表刊物：JOURNAL OF ORGANOMETALLIC CHEMISTRY
收录刊物：SCIE、EI、Scopus
卷号：691
期号：22
页面范围：4633-4640
ISSN号：0022-328X
关键字：bioinorganic chemistry; Fe-only hydrogenase; spectroelectrochemistry; phosphine ligand
摘要：A tris(N-pyrrolidinyl)phosphine (P(NC4H8)(3)) monosubstituted complex, [(mu-pdt)Fe-2(CO)(5)P(NC4H8)(3)] (2) was synthesized as a functional model of the hydrogen-producing capability of the iron hydrogenase active site. The structure was fully characterized by X-ray crystallography. IR and electrochemical studies have indicated that the P(NC4H8)(3) ligand has better electron-donating ability than that of those phosphine ligands, such as PMe3, PTA (1,3,5-triaza-7-phosphaadamantane), PMe2Ph PPh3, and P(OEt)(3). The electrocatalytic activity of 2 was recorded in CH3CN in the absence and presence of weak acid, HOAc. The cathodic shift of potential at -1.98 V and the dependence of current on acid concentration have indicated that complex 2 can catalyze the reduction of protons to hydrogen at its (FeFe1)-Fe-0 level in the presence of HOAc. IR spectroelectrochemical experiments are conducted during the reduction of 2 under nitrogen and carbon monoxide, respectively. The formation of a bridging CO group during the reduction of 2 at -1.98 V has been identified using IR spectroelectrochemical techniques, and an electrocatalytic mechanism of 2 consistent with the spectroscopic and electrochemical results is proposed. (c) 2006 Elsevier B.V. All rights reserved.