0517835 - ÚOCHB 2020 RIV GB eng J - Journal Article
Maldonado-Domínguez, M. - Bím, Daniel - Fučík, R. - Čurík, R. - Srnec, M.
Reactive mode composition factor analysis of transition states: The case of coupled electron-proton transfers.
Physical Chemistry Chemical Physics. Roč. 21, č. 45 (2019), s. 24912-24918. ISSN 1463-9076. E-ISSN 1463-9084
Institutional support: RVO:61388963
Keywords : electron-proton transfers * transition states * chemical reactivity
OECD category: Physical chemistry
Impact factor: 3.430, year: 2019
Method of publishing: Limited access
https://pubs.rsc.org/en/content/articlelanding/2019/CP/C9CP05131G#!divAbstract

A simple method for the evaluation of the kinetic energy distribution within the reactive mode of a transition state (TS), denoted as the Reactive Mode Composition Factor (RMCF), is presented. It allows one to directly map the barrier properties onto the atomic-motion components of the reaction coordinate at the TS, which has potential to shed light onto some mechanistic features of a chemical process. To demonstrate the applicability of RMCF to reactivity, we link the kinetic energy distribution within a reactive mode with the asynchronicity (η) in C–H bond activation, as they both evolve in a series of coupled proton–electron transfer (CPET) reactions between FeIVO oxidants and 1,4-cyclohexadiene. RMCF shows how the earliness or lateness of a process manifests as a redistribution of kinetic energy in the reactive mode as a function of the free energy of reaction (ΔG0) and η. Finally, the title analysis can be applied to predict H-atom tunneling contributions and kinetic isotope effects in a set of reactions, yielding a transparent rationalization based on the kinetic energy distributions in the reactive mode.
Permanent Link: http://hdl.handle.net/11104/0303099