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

Benjamin Rudshteyn, Katherine J. Fisher, Hannah M.C. Lant, Ke R. Yang, Brandon Q. Mercado, Gary W Brudvig, Robert H. Crabtree, Victor S. Batista

Research output: Contribution to journalArticle

8 Citations (Scopus)

Abstract

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.

Original languageEnglish
Pages (from-to)7952-7960
Number of pages9
JournalACS Catalysis
Volume8
Issue number9
DOIs
Publication statusPublished - Sep 7 2018

Fingerprint

Isotopes
Oxidation
Catalysts
Water
Deprotonation
Nucleophiles
Kinetics
Density functional theory
Metals
Oxygen
Derivatives
Substrates

Keywords

  • catalysis
  • copper
  • density functional theory
  • electrocatalysis
  • water oxidation
  • water-nucleophilic attack

ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)

Cite this

Rudshteyn, B., Fisher, K. J., Lant, H. M. C., Yang, K. R., Mercado, B. Q., Brudvig, G. W., ... Batista, V. S. (2018). Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst. ACS Catalysis, 8(9), 7952-7960. https://doi.org/10.1021/acscatal.8b02466

Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst. / Rudshteyn, Benjamin; Fisher, Katherine J.; Lant, Hannah M.C.; Yang, Ke R.; Mercado, Brandon Q.; Brudvig, Gary W; Crabtree, Robert H.; Batista, Victor S.

In: ACS Catalysis, Vol. 8, No. 9, 07.09.2018, p. 7952-7960.

Research output: Contribution to journalArticle

Rudshteyn, B, Fisher, KJ, Lant, HMC, Yang, KR, Mercado, BQ, Brudvig, GW, Crabtree, RH & Batista, VS 2018, 'Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst', ACS Catalysis, vol. 8, no. 9, pp. 7952-7960. 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. ; Batista, Victor S. / Water-Nucleophilic Attack Mechanism for the CuII(pyalk)2 Water-Oxidation Catalyst. In: ACS Catalysis. 2018 ; Vol. 8, No. 9. pp. 7952-7960.
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