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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
Mono- and binuclear complexes of iron(II) and iron(III) with an N4O ligand: synthesis, structures and catalytic properties in alkane oxidation
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论文类型：期刊论文
发表时间：2006-05-28
发表刊物：DALTON TRANSACTIONS
收录刊物：SCIE、EI、PubMed、Scopus
期号：20
页面范围：2427-2434
ISSN号：1477-9226
摘要：Three mononuclear iron complexes and one binuclear iron complex, [Fe(tpoen)Cl]center dot 0.5(Fe2OCl6) (1), [Fe(tpoen)Cl]PF6 (2), Fe(tpoen)Cl-3 (3) and [{Fe(tpoen)}(2)(mu-O)](ClO4)(4) (4) (tpoen = N-(2-pyridylmethoxyethyl)-N,N-bis(2-pyridylmethyl)amine), were synthesized as functional models of non-heme iron oxygenases. Crystallographic studies revealed that the Fe(II) center of 1 is in a pseudooctahedral environment with a pentadentate N4O ligand and a chloride ion trans to the oxygen atom. The Fe(III) center of 3 is ligated by three nitrogen atoms of tpoen and three chloride ions in a facial configuration. Each Fe(III) center of 4 is coordinated with four nitrogen atoms and an oxygen atom of tpoen with the Fe-O-Fe angle of 172.0(3) angstrom. Complexes 2, 3 and 4 catalysed the oxidation of cyclohexane with H2O2 in the total TNs of 24 - 36 with A/K ratios of 1.9-2.4. Under the same conditions they also catalysed both the oxidation of ethylbenzene to benzylic alcohol and acetobenzene with good activity (30-47 TN) and low selectivity (A/K 0.7), and the oxidation of adamantane with moderate activity (15-18 TN) and low regioselectivity (3 degrees/2 degrees 3.0-3.2). With mCPBA as oxidant the catalytic activities of 2, 3 and 4 increased 1.8 to 2.3-fold for the oxidation of cyclohexane and ethylbenzene and 6.3 to 7.5-fold for the oxidation of adamantane. Drastic enhancement of the regioselectivity was observed in the oxidation of adamantane (3 degrees/2 degrees 18.5-30.3).