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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
Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a 2,2 '-Bipyridine-6,6 '-dicarboxylate (bda) Ligand: How Ligand Environment Influences the Catalytic Behavior
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论文类型：期刊论文
发表时间：2014-02-03
发表刊物：INORGANIC CHEMISTRY
收录刊物：SCIE、Scopus
卷号：53
期号：3
页面范围：1307-1319
ISSN号：0020-1669
摘要：A new water oxidation catalyst [Ru-III(bda)(mmi)(OH2)]-(CF3SO3) (2, H(2)bda = 2,2 '-bipyridine-6,6 '-dicarboxylic acid; mmi = 1,3-dimethylimidazolium-2-ylidene) containing an axial N-heterocyclic carbene ligand and one aqua ligand was synthesized and fully characterized. The kinetics of catalytic water oxidation by 2 were measured using stopped-flow technique, and key intermediates in the catalytic cycle were probed by density functional theory calculations. While analogous Ru-bda water oxidation catalysts [Ru(bda)L-2] (L = pyridyl ligands) are supposed to catalyze water oxidation through a bimolecular coupling pathway, our study points out that 2, surprisingly, undergoes a single-site water nucleophilic attack (acid-base) pathway. The diversion of catalytic mechanisms is mainly ascribed to the different ligand environments, from nonaqua ligands to an aqua ligand. Findings in this work provide some critical proof for our previous hypothesis about how alternation of ancillary ligands of water oxidation catalysts influences their catalytic efficiency.