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submitted on 06.10.2020 and posted on 07.10.2020by 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.