Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex
Abstract
The high-valent nickel(III) complex Ni(pyalk)2+ (2) was prepared by oxidation of a nickel(II) complex, Ni(pyalk)2 (1) (pyalk = 2-pyridyl-2-propanoate). 2 and derivatives were fully characterized by mass spectrometry and X-ray crystallography. Electron paramagnetic resonance spectroscopy and X-ray photoelectron spectroscopy confirm that the oxidation is metal-centered. 2 was found to react with a variety of phenolic and hydrocarbon substrates. A linear correlation between the measured rate constant and the substrate bond dissociation enthalpy (BDE) was found for both phenolic and hydrocarbon substrates. Large H/D kinetic isotope effects were also observed for both sets of substrates. These results suggest that 2 reacts through concerted proton-electron transfer (CPET). Analysis of measured thermodynamic parameters allows us to calculate a bond dissociation free energy (BDFE) of ~91 kcal mol–1 for the O–H bond of the bound pyalk ligand. These findings may shed light onto CPET steps in oxidative catalysis and have implications for ligand design in catalytic systems.
- Authors:
-
- Department of Chemistry, Yale University, New Haven, USA
- Publication Date:
- Research Org.:
- Northwestern Univ., Evanston, IL (United States); Energy Frontier Research Centers (EFRC) (United States). Center for Light Energy Activated Redox Processes (LEAP)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division; National Science Foundation (NSF)
- OSTI Identifier:
- 1582476
- Alternate Identifier(s):
- OSTI ID: 1624985
- Grant/Contract Number:
- SC0001059; DGE1122492
- Resource Type:
- Published Article
- Journal Name:
- Chemical Science
- Additional Journal Information:
- Journal Name: Chemical Science Journal Volume: 11 Journal Issue: 6; Journal ID: ISSN 2041-6520
- Publisher:
- Royal Society of Chemistry (RSC)
- Country of Publication:
- United Kingdom
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; Chemistry
Citation Formats
Fisher, Katherine J., Feuer, Margalit L., Lant, Hannah M. C., Mercado, Brandon Q., Crabtree, Robert H., and Brudvig, Gary W. Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex. United Kingdom: N. p., 2020.
Web. doi:10.1039/C9SC05565G.
Fisher, Katherine J., Feuer, Margalit L., Lant, Hannah M. C., Mercado, Brandon Q., Crabtree, Robert H., & Brudvig, Gary W. Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex. United Kingdom. https://doi.org/10.1039/C9SC05565G
Fisher, Katherine J., Feuer, Margalit L., Lant, Hannah M. C., Mercado, Brandon Q., Crabtree, Robert H., and Brudvig, Gary W. Wed .
"Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex". United Kingdom. https://doi.org/10.1039/C9SC05565G.
@article{osti_1582476,
title = {Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex},
author = {Fisher, Katherine J. and Feuer, Margalit L. and Lant, Hannah M. C. and Mercado, Brandon Q. and Crabtree, Robert H. and Brudvig, Gary W.},
abstractNote = {The high-valent nickel(III) complex Ni(pyalk)2+ (2) was prepared by oxidation of a nickel(II) complex, Ni(pyalk)2 (1) (pyalk = 2-pyridyl-2-propanoate). 2 and derivatives were fully characterized by mass spectrometry and X-ray crystallography. Electron paramagnetic resonance spectroscopy and X-ray photoelectron spectroscopy confirm that the oxidation is metal-centered. 2 was found to react with a variety of phenolic and hydrocarbon substrates. A linear correlation between the measured rate constant and the substrate bond dissociation enthalpy (BDE) was found for both phenolic and hydrocarbon substrates. Large H/D kinetic isotope effects were also observed for both sets of substrates. These results suggest that 2 reacts through concerted proton-electron transfer (CPET). Analysis of measured thermodynamic parameters allows us to calculate a bond dissociation free energy (BDFE) of ~91 kcal mol–1 for the O–H bond of the bound pyalk ligand. These findings may shed light onto CPET steps in oxidative catalysis and have implications for ligand design in catalytic systems.},
doi = {10.1039/C9SC05565G},
journal = {Chemical Science},
number = 6,
volume = 11,
place = {United Kingdom},
year = {2020},
month = {2}
}
https://doi.org/10.1039/C9SC05565G
Web of Science
Figures / Tables:

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