Concerted Proton-electron Transfer Oxidation of Phenols and Hydrocarbons by a High-valent Nickel Complex

Overview

Journal Chem Sci

Publisher Royal Society of Chemistry

Specialty Chemistry

Date 2020 Mar 25

PMID 32206289

Citations 5

Authors

Katherine J Fisher

Margalit L Feuer

Hannah M C Lant

Brandon Q Mercado

Robert H Crabtree

Gary W Brudvig

Affiliations

Soon will be listed here.

Abstract

The high-valent nickel(iii) complex Ni(pyalk) () was prepared by oxidation of a nickel(ii) complex, Ni(pyalk) () (pyalk = 2-pyridyl-2-propanoate). 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. 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 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 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.

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