Commun. Comput. Chem., 7 (2025), pp. 145-151.
Published online: 2025-06
[An open-access article; the PDF is free to any online user.]
Cited by
- BibTex
- RIS
- TXT
This work employed DFT calculations to elucidate the mechanism of water oxidation reaction catalyzed by a mononuclear pyridine-based copper complex, which was reported to be a homogeneous water oxidation catalyst in a pH=11.84 buffer solution. The coordination of one water molecule with the ${\rm Cu}^{{\rm II}}$ center leads to the generation of the ${\rm Cu}^{{\rm II}}-{\rm OH}_2 (1-{\rm H}_2{\rm O}).$ The active species $({\rm Cu}^{{\rm IV}}={\rm O, 3})$ is generated after two subsequent proton-coupled electron transfer processes from $1-{\rm H}_2{\rm O}.$ $3$ triggers the O-O bond formation via water nucleophilic attack mechanism. The triplet ${\rm O}_2$ can be released after following two oxidation processes. The formation of the O-O bond is the rate-determining step for the catalytic cycle associated with a total barrier of 19.3 kcal/mol.
}, issn = {2617-8575}, doi = {https://doi.org/10.4208/cicc.2025.49.01}, url = {http://global-sci.org/intro/article_detail/cicc/24184.html} }This work employed DFT calculations to elucidate the mechanism of water oxidation reaction catalyzed by a mononuclear pyridine-based copper complex, which was reported to be a homogeneous water oxidation catalyst in a pH=11.84 buffer solution. The coordination of one water molecule with the ${\rm Cu}^{{\rm II}}$ center leads to the generation of the ${\rm Cu}^{{\rm II}}-{\rm OH}_2 (1-{\rm H}_2{\rm O}).$ The active species $({\rm Cu}^{{\rm IV}}={\rm O, 3})$ is generated after two subsequent proton-coupled electron transfer processes from $1-{\rm H}_2{\rm O}.$ $3$ triggers the O-O bond formation via water nucleophilic attack mechanism. The triplet ${\rm O}_2$ can be released after following two oxidation processes. The formation of the O-O bond is the rate-determining step for the catalytic cycle associated with a total barrier of 19.3 kcal/mol.