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Statistical Analysis of C–H Activation by Transition Metal Oxo Species Supports Thermodynamic Control Over Reactivity

submitted on 06.10.2020, 13:33 and posted on 07.10.2020, 04:53 by Joseph Schneider, McKenna Goetz, John Anderson
Transition metal oxo species are key intermediates for the activation of strong C‒H bonds. As such, there has been interest in understanding which structural or electronic parameters of metal oxo complexes determine their reactivity. Factors such as ground state thermodynamics, spin state, steric environment, oxygen radical character, and asynchronicity have all been cited as key contributors, yet there is no consensus on when each of these parameters is significant or the relative magnitude of their effects. Herein, we present a thorough statistical analysis of parameters that have been proposed to influence transition metal oxo mediated C‒H activation. We used density functional theory (DFT) to compute parameters for transition metal oxo complexes and analyzed their ability to explain and predict an extensive data set of experimentally determined reaction barriers. We found that, in general, only thermodynamic parameters related to the free energy of hydrogen atom, proton, and electron transfer play a statistically significant role.


NIH R35 GM133470

CAREER: Probing Catalytic O-O Bond Formation with Psuedo-Tetrahedral Terminal Oxo Complexes

Directorate for Mathematical & Physical Sciences

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DoD NDSEG 00003765

Sloan Foundation FG-2019-11497


Email Address of Submitting Author


University of Chicago


United States

ORCID For Submitting Author


Declaration of Conflict of Interest