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Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex

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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.

Graphical abstract: Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex

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Article information


Submitted
03 Nov 2019
Accepted
29 Dec 2019
First published
06 Jan 2020

This article is Open Access
All publication charges for this article have been paid for by the Royal Society of Chemistry

Chem. Sci., 2020, Advance Article
Article type
Edge Article

Concerted proton-electron transfer oxidation of phenols and hydrocarbons by a high-valent nickel complex

K. J. Fisher, M. L. Feuer, H. M. C. Lant, B. Q. Mercado, R. H. Crabtree and G. W. Brudvig, Chem. Sci., 2020, Advance Article , DOI: 10.1039/C9SC05565G

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