Isolation and Identification of Pseudo Seven-Coordinate Ru(Ⅲ)Intermediate Completing the Catalytic Cycle of Ru-bda Type of Water Oxidation Catalysts  

作　　者：Tianqi Liu Ge Li Nannan Shen Linqin Wang Brian J.J.Timmer Shengyang Zhou Biaobiao Zhang Alexander Kravchenko Bo Xu Marten S.G.Ahlquist Licheng Sun 

机构地区：[1]Department of Chemistry,School of Engineering Sciences in Chemistry,Biotechnology,and Health,KTH Royal Institute of Technology,Stockholm 10044 [2]Department of Theoretical Chemistry and Biology,School of Engineering Sciences in Chemistry,Biotechnology,and Health,KTH Royal Institute of Technology,Stockholm 10691 [3]State Key Laboratory of Radiation Medicine and Protection,School for Radiological and Interdisciplinary Sciences(RAD-X),Collaborative Innovation Center of Radiation Medicine of Jiangsu Higher Education Institutions,Soochow University,Suzhou 215123 [4]Center of Artificial Photosynthesis for Solar Fuels,School of Science,Westlake University,Hangzhou 310024 [5]Nanotechnology and Functional Materials,Department of Materials Sciences and Engineering,The Angstrom Laboratory,Uppsala University,Uppsala 75103 [6]Institute of Artificial Photosynthesis(IAP),State Key Laboratory of Fine Chemicals,Dalian University of Technology(DUT),Dalian 116024

出　　处：《CCS Chemistry》2022年第7期2481-2490,共10页中国化学会会刊（英文）

基　　金：financially supported by the Swedish Research Council(2017-00935);the Knut and Alice Wallenberg Foundation(KAW 2016.0072);the China Scholarship Council(CSC).

摘　　要：Isolation of RuⅢ-bda(17-electron specie)complex with an aqua ligand(2-electron donor)is challenging due to violation of the 18-electron rule.Although considerable efforts have been dedicated to mechanistic studies of water oxidation by the Ru-bda family,the structure and initial formation of the Ru^(Ⅲ)-bda aqua complex are still controversial.Herein,we challenge this often overlooked step by designing a pocketshape Ru-based complex 1.The computational studies showed that 1 possesses the crucial hydrophobicity at the Ru^(V)(O)state as well as similar probability of access of terminal O to solvent water molecules when compared with classic Ru-bda catalysts.Through characterization of single-crystal structures at the Ru^(Ⅱ) and Ru^(Ⅲ) states,a pseudo seven-coordinate“ready-togo”aqua ligand with Ru^(Ⅲ)…O distance of 3.62A was observed.This aqua ligand was also found to be part of a formed hydrogen-bonding network,providing a good indication of how the Ru^(Ⅲ)-OH_(2)complex is formed.

关 键 词：Ru-bda water oxidation pseudo seven-coordinate Ru^(Ⅲ)-OH_(2)intermediate water preorganization 

分 类 号：O643.36[理学—物理化学]