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Title: 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:
 [1];  [1];  [1];  [1]; ORCiD logo [1]; ORCiD logo [1]
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  1. 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.
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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
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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.
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@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}
}
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https://doi.org/10.1039/C9SC05565G
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Figures / Tables:

Fig. 1 Fig. 1: (Left) X-ray crystal structure of Ni(pyalk)2 (1). Atoms are shown at the 50% probability level (1). (Right) Cyclic voltammogram of 1 in MeCN. The reversible wave at 0.15 V vs. Fc/Fc+ is assigned as a Ni(II/III) couple.
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