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Isolation and identification of pseudo seven-coordinate Ru(iii) intermediate completing the catalytic cycle of Ru-bda type of water oxidation catalysts

DOI: 10.31635/ccschem.021.202101159 DOI Help

Authors: Tianqi Liu (KTH Royal Institute of Technology) , Ge Li (KTH Royal Institute of Technology) , Nannan Shen (Soochow University) , Linqin Wang (Westlake University) , Brian J. J. Timmer (KTH Royal Institute of Technology) , Shengyang Zhou (The Ångström Laboratory) , Biaobiao Zhang (Westlake University) , Alexander Kravchenko (KTH Royal Institute of Technology) , Bo Xu (KTH Royal Institute of Technology) , Mårten S. G. Ahlquist (KTH Royal Institute of Technology) , Licheng Sun (KTH Royal Institute of Technology; Westlake University; Dalian University of Technology (DUT))
Co-authored by industrial partner: No

Type: Journal Paper
Journal: Ccs Chemistry

State: Published (Approved)
Published: August 2021
Diamond Proposal Number(s): 20805

Open Access Open Access

Abstract: 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 many efforts have been dedicated to mechanistic studies of water oxidation by the Ru-bda family, the structure and initial formation of RuIII-bda aqua complex are still controversial. Here we challenged this often overlooked step by design of a pocket-shaped Ru-based complex 1. The computational studies showed 1 hold the crucial hydrophobicity at RuV(O) state as well as the similar access probability 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.

Journal Keywords: Ru-bda; water oxidation; pseudo seven-coordinate; RuIII-OH2 intermediate; water preorganization

Subject Areas: Chemistry, Energy


Instruments: I19-Small Molecule Single Crystal Diffraction

Added On: 14/08/2021 22:12

Documents:
ccschem.021.202101159.pdf

Discipline Tags:

Energy Storage Energy Physical Chemistry Catalysis Chemistry Inorganic Chemistry

Technical Tags:

Diffraction Single Crystal X-ray Diffraction (SXRD)