气候变化领域集成服务门户(CCPortal): Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles

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DOI	10.1039/c7ee01557g
	Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles
	Kunz V.; Lindner J.O.; Schulze M.; Röhr M.I.S.; Schmidt D.; Mitrić R.; Würthner F.
发表日期	2017
ISSN	17545692
起始页码	2137
结束页码	2153
卷号	10 期号:10
英文摘要	A series of trinuclear metallosupramolecular Ru(bda) macrocycles has been synthesized and the impact of the ring size on the catalytic activity in homogeneous water oxidation has been elucidated (bda = 2,2′-bipyridine-6,6′-dicarboxylate). Kinetic experiments revealed that for all macrocyclic catalysts a proton-coupled oxidation event is rate-determining. Distinct H/D kinetic isotope effects (KIE) have been observed for the individual macrocycles, which follow the same tendency like the catalytic activity where an intermediate ring size exhibits the best performance. To get insight into the different molecular properties, molecular dynamics simulations using a QM/MM approach have been performed for all reaction steps, revealing that the size of the cavity strongly influences the hydrogen-bonded water network inside the macrocyclic structure and thus, important proton-coupled reaction steps of the catalytic cycle. For the most active catalysts, all reactive sites point into the interior of the cavity, which is supported by a single crystal X-ray analysis of the largest macrocycle, and a cooperative effect between the individual Ru(bda) centers facilitating proton abstraction has been substantiated. On the other hand, different structural conformations predominate the smaller macrocycles, which prevent efficient interactions between the Ru(bda) centers. © The Royal Society of Chemistry.
英文关键词	Carboxylation; Catalysts; Catalytic oxidation; Hydrogen bonds; Molecular dynamics; Oxidation; Reaction kinetics; Ruthenium; Single crystals; Supramolecular chemistry; X ray analysis; Co-operative effects; Efficient interaction; Kinetic isotope effects; Macrocyclic structure; Metallo-supramolecular; Molecular dynamics simulations; Single crystal X-ray analysis; Structural conformations; Catalyst activity; catalysis; crystal; molecular analysis; oxidation; performance assessment; reaction kinetics; ruthenium; X-ray spectroscopy
语种	英语
来源期刊	Energy & Environmental Science
文献类型	期刊论文
条目标识符	http://gcip.llas.ac.cn/handle/2XKMVOVA/190393
作者单位	Institut für Organische Chemie, Universität Würzburg Am Hubland, Würzburg, 97074, Germany; Institut für Physikalische und Theoretische Chemie, Universität Würzburg, Emil-Fischer-Str. 42, Würzburg, 97074, Germany; Center for Nanosystems Chemistry (CNC), Universität Würzburg Theodor-Boveri-Weg, Würzburg, 97074, Germany
推荐引用方式 GB/T 7714	Kunz V.,Lindner J.O.,Schulze M.,et al. Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles[J],2017,10(10).
APA	Kunz V..,Lindner J.O..,Schulze M..,Röhr M.I.S..,Schmidt D..,...&Würthner F..(2017).Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles.Energy & Environmental Science,10(10).
MLA	Kunz V.,et al."Cooperative water oxidation catalysis in a series of trinuclear metallosupramolecular ruthenium macrocycles".Energy & Environmental Science 10.10(2017).