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Title: Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst

Abstract

Here, we investigate the mechanism of water oxidation catalyzed by the CuII(pyalk)2 complex, combining density functional theory with experimental measurements of turnover frequencies, UV–visible spectra, H/D kinetic isotope effects (KIEs), electrochemical analysis, and synthesis of a derivative complex. We find that only in the cis form does CuII(pyalk)2 convert water to dioxygen. In a series of alternating chemical and electrochemical steps, the catalyst is activated to form a metal oxyl radical species that undergoes a water-nucleophilic attack defining the rate-limiting step of the reaction. The experimental H/D KIE (3.4) is in agreement with the calculated value (3.7), shown to be determined by deprotonation of the substrate nucleophile upon O–O bond formation. The reported mechanistic findings are particularly valuable for rational design of complexes inspired by CuII(pyalk)2.

Authors:
ORCiD logo [1];  [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [1]
  1. Yale Univ., New Haven, CT (United States)
Publication Date:
Research Org.:
Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). National Energy Research Scientific Computing Center (NERSC); Northwestern Univ., Evanston, IL (United States)
Sponsoring Org.:
USDOE Office of Science (SC)
OSTI Identifier:
1543705
Grant/Contract Number:  
SC0001059
Resource Type:
Accepted Manuscript
Journal Name:
ACS Catalysis
Additional Journal Information:
Journal Volume: 8; Journal Issue: 9; Journal ID: ISSN 2155-5435
Publisher:
American Chemical Society (ACS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; chemistry; water oxidation; catalysis; copper; water-nucleophilic attack; density functional theory; electrocatalysis

Citation Formats

Rudshteyn, Benjamin, Fisher, Katherine J., Lant, Hannah M. C., Yang, Ke R., Mercado, Brandon Q., Brudvig, Gary W., Crabtree, Robert H., and Batista, Victor S. Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst. United States: N. p., 2018. Web. doi:10.1021/acscatal.8b02466.
Rudshteyn, Benjamin, Fisher, Katherine J., Lant, Hannah M. C., Yang, Ke R., Mercado, Brandon Q., Brudvig, Gary W., Crabtree, Robert H., & Batista, Victor S. Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst. United States. doi:https://doi.org/10.1021/acscatal.8b02466
Rudshteyn, Benjamin, Fisher, Katherine J., Lant, Hannah M. C., Yang, Ke R., Mercado, Brandon Q., Brudvig, Gary W., Crabtree, Robert H., and Batista, Victor S. Wed . "Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst". United States. doi:https://doi.org/10.1021/acscatal.8b02466. https://www.osti.gov/servlets/purl/1543705.
@article{osti_1543705,
title = {Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst},
author = {Rudshteyn, Benjamin and Fisher, Katherine J. and Lant, Hannah M. C. and Yang, Ke R. and Mercado, Brandon Q. and Brudvig, Gary W. and Crabtree, Robert H. and Batista, Victor S.},
abstractNote = {Here, we investigate the mechanism of water oxidation catalyzed by the CuII(pyalk)2 complex, combining density functional theory with experimental measurements of turnover frequencies, UV–visible spectra, H/D kinetic isotope effects (KIEs), electrochemical analysis, and synthesis of a derivative complex. We find that only in the cis form does CuII(pyalk)2 convert water to dioxygen. In a series of alternating chemical and electrochemical steps, the catalyst is activated to form a metal oxyl radical species that undergoes a water-nucleophilic attack defining the rate-limiting step of the reaction. The experimental H/D KIE (3.4) is in agreement with the calculated value (3.7), shown to be determined by deprotonation of the substrate nucleophile upon O–O bond formation. The reported mechanistic findings are particularly valuable for rational design of complexes inspired by CuII(pyalk)2.},
doi = {10.1021/acscatal.8b02466},
journal = {ACS Catalysis},
number = 9,
volume = 8,
place = {United States},
year = {2018},
month = {7}
}

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