期刊
CCS CHEMISTRY
卷 4, 期 7, 页码 2481-2490出版社
CHINESE CHEMICAL SOC
DOI: 10.31635/ccschem.021.202101159
关键词
Ru-bda; water oxidation; pseudo seven-coordinate; Ru-III-OH2 intermediate; water preorganization
资金
- Swedish Research Council [2017-00935]
- Knut and Alice Wallenberg Foundation [KAW 2016.0072]
- China Scholarship Council (CSC)
This article investigates the structure and formation process of the Ru-III-bda complex. By designing a pocketshape Ru-based complex and conducting computational studies and single-crystal structure characterization, a Ru-III...O distance of 3.62 A for the aqua ligand was observed, and it was found to be part of a formed hydrogen-bonding network, providing clues for the formation of the Ru-III-OH2 complex.
Isolation of Ru-III-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-to-go aqua ligand with Ru-III...O distance of 3.62 A 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-OH2 complex is formed. [GRAPHICS] .
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