Citation: Ying-Ying Li, Rong-Zhen Liao. Mechanism of water oxidation catalyzed by vitamin B₁₂: Redox non-innocent nature of corrin ligand and crucial role of phosphate[J]. Chinese Chemical Letters, ;2022, 33(1): 358-361. doi: 10.1016/j.cclet.2021.06.028 shu

Mechanism of water oxidation catalyzed by vitamin B₁₂: Redox non-innocent nature of corrin ligand and crucial role of phosphate

Ying-Ying Li ,
Rong-Zhen Liao ^*,

Key Laboratory of Material Chemistry for Energy Conversion and Storage, Ministry of Education, Hubei Key Laboratory of Bioinorganic Chemistry and Materia Medica, Hubei Key Laboratory of Materials Chemistry and Service Failure, School of Chemistry and Chemical Engineering, Huazhong University of Science and Technology, Wuhan 430074, China

rongzhen@hust.edu.cn

Received Date: 6 April 2021
Revised Date: 30 May 2021
Accepted Date: 9 June 2021
Available Online: 16 June 2021

Figures(3)

Vitamin B₁₂ (macrocyclic cobalamin) has been recently reported to be capable of electrochemically catalyzing water oxidation in a neutral phosphate buffer solution. In this work, density functional calculations were employed to elucidate the water oxidation mechanism catalyzed by vitamin B₁₂. The calculations showed that the catalytic cycle starts from the L^•-Co^II-OH₂ complex 1. A proton-coupled electron transfer process then leads to the formation of a L^•-Co^III-OH complex 2, followed by another proton-coupled electron transfer event to afford a corrin ligand radical cation intermediate 3 (L^•-Co^III-O^•). The redox non-innocent nature of the corrin ligand plays an essential role in the oxidation process. 3 is capable of triggering the O-O bond formation via a water nucleophilic attack mechanism, in which a hydrophosphate dianion functions as a base to accept a proton from the water nucleophile. A dioxygen molecule is released after the oxidation of the Co^III-OOH intermediate. The rate-determining step was calculated to be the O-O bond formation with a total barrier of 16.5 kcal/mol. While the use of water molecules as the proton acceptor was found to be less feasible for the O-O bond formation, with a barrier of 31.2 kcal/mol, further highlighting the crucial of phosphate in water oxidation.
- Water oxidation,
- DFT calculations,
- Mechanism,
- Vitamin B₁₂,
- Cobalt
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Mechanism of water oxidation catalyzed by vitamin B12: Redox non-innocent nature of corrin ligand and crucial role of phosphate

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Mechanism of water oxidation catalyzed by vitamin B₁₂: Redox non-innocent nature of corrin ligand and crucial role of phosphate