Isolation and Identification of Pseudo Seven-Coordinate Ru(III) Intermediate Completing the Catalytic Cycle of Ru-bda Type of Water Oxidation Catalysts
| Autor: | Mårten S. G. Ahlquist, Shengyang Zhou, Biaobiao Zhang, Ge Li, Brian J. J. Timmer, Linqin Wang, Bo Xu, Nannan Shen, Licheng Sun, Tianqi Liu, Alexander Kravchenko |
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| Rok vydání: | 2022 |
| Předmět: |
Organisk kemi
Nanoteknik RuIII-OH2 intermediate Chemistry Ligand Organic Chemistry General Engineering water preorganization General Chemistry Combinatorial chemistry Catalysis water oxidation Catalytic cycle Ru-bda Teknik och teknologier Naturvetenskap Engineering and Technology Nano Technology Natural Sciences pseudo seven-coordinate |
| Zdroj: | CCS Chemistry. 4:2481-2490 |
| ISSN: | 2096-5745 |
| DOI: | 10.31635/ccschem.021.202101159 |
| Popis: | 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 RuIII-bda aqua complex are still controversial. Herein, we challenge this often overlooked step by designing a pocket-shape Ru-based complex 1. The computational studies showed that 1 possesses the crucial hydrophobicity at the RuV(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 RuII and RuIII states, a pseudo seven-coordinate “ready-to-go” aqua ligand with RuIII...O distance of 3.62 Å was observed. This aqua ligand was also found to be part of a formed hydrogen-bonding network, providing a good indication of how the RuIII-OH2 complex is formed. QC 20220811 |
| Databáze: | OpenAIRE |
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