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论文类型：期刊论文

发表时间：2017-09-01

发表刊物：COORDINATION CHEMISTRY REVIEWS

收录刊物：SCIE、Scopus

卷号：346

期号：,SI

页面范围：206-215

ISSN号：0010-8545

关键字：Water oxidation; EPR; Ruthenium; Coordination; DFT

摘要：The coordination of a substrate water molecule on a metal centered catalyst for water oxidation is a crucial step involving the reorganization of the ligand sphere. This process can occur by substituting a coordinated ligand with a water molecule or via a direct coordination of water onto an open site. In 2009, we reported an efficient ruthenium-based molecular catalyst, Ru-bda, for water oxidation. Despite the impressive improvement in catalytic activity of this type of catalyst over the past years, a lack of understanding of the water coordination still remains. Herein, we report our EPR and DFT studies on Ru-bda (triethylammonium 3-pyridine sulfonate)(2) (1) at its Ru-III oxidation state, which is the initial state in the catalytic cycle for the O-O bond formation. Our investigation suggests that at this III-state, there is already a rearrangement in the ligand sphere where the coordination of a water molecule at the 7th position (open site) takes place under acidic conditions (pH = 1.0) to form a rare 7-coordinated Ru-III species. (C) 2017 Elsevier B.V. All rights reserved.