Chemical and Photochemical Water Oxidation Catalyzed by Mononuclear Ruthenium Complexes with a Negatively Charged Tridentate Ligand |
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| Authors: | Lele Duan Yunhua Xu Dr Mikhail Gorlov Dr Lianpeng Tong Samir Andersson Licheng Sun Prof |
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| Institution: | 1. Department of Chemistry, Royal Institute of Technology (KTH), Teknikringen 30, 10044 Stockholm (Sweden);2. DUT‐KTH Joint Education and Research Center on Molecular Devices, State Key Laboratory of Fine Chemicals, Dalian University of Technology (DUT), 116012 Dalian (China), Fax: (+46)?8‐7912333 |
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| Abstract: | Two mononuclear ruthenium complexes RuL(pic)3] ( 1 ) and RuL(bpy)(pic)] ( 2 ) (H2L=2,6‐pyridinedicarboxylic acid, pic=4‐picoline, bpy=2,2′‐bipyridine) have been synthesized and fully characterized. Both complexes could promote water oxidation chemically and photochemically. Compared with other known ruthenium‐based water oxidation catalysts using Ce(NH4)2(NO3)6] (CeIV) as the oxidant in solution at pH 1.0, complex 1 is one of the most active catalysts yet reported with an initial rate of 0.23 turnover s?1. Under acidic conditions, the equatorial 4‐picoline in complex 1 dissociates first. In addition, ligand exchange in 1 occurs when the RuIII state is reached. Based on the above observations and MS measurements of the intermediates during water oxidation by 1 using CeIV as oxidant, RuL(pic)2(H2O)]+ is proposed as the real water oxidation catalyst. |
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| Keywords: | electrochemistry homogeneous catalysis oxidation ruthenium water splitting |
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