In:
Proceedings of the National Academy of Sciences, Proceedings of the National Academy of Sciences, Vol. 118, No. 52 ( 2021-12-28)
Abstract:
The understanding of O–O bond formation is of great importance for revealing the mechanism of water oxidation in photosynthesis and for developing efficient catalysts for water oxidation in artificial photosynthesis. The chemical oxidation of the Ru II 2 (OH)(OH 2 ) core with the vicinal OH and OH 2 ligands was spectroscopically and theoretically investigated to provide a mechanistic insight into the O–O bond formation in the core. We demonstrate O–O bond formation at the low-valent Ru III 2 (OH) core with the vicinal OH ligands to form the Ru II 2 (μ-OOH) core with a μ-OOH bridge. The O–O bond formation is induced by deprotonation of one of the OH ligands of Ru III 2 (OH) 2 via intramolecular coupling of the OH and deprotonated O − ligands, conjugated with two-electron transfer from two Ru III centers to their ligands. The intersystem crossing between singlet and triple states of Ru II 2 (μ-OOH) is easily switched by exchange of H + between the μ-OOH bridge and the auxiliary backbone ligand.
Type of Medium:
Online Resource
ISSN:
0027-8424
,
1091-6490
DOI:
10.1073/pnas.2113910118
Language:
English
Publisher:
Proceedings of the National Academy of Sciences
Publication Date:
2021
detail.hit.zdb_id:
209104-5
detail.hit.zdb_id:
1461794-8
SSG:
11
SSG:
12
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