scholarly journals Dichotomous Hydrogen Atom Transfer vs Proton-Coupled Electron Transfer During Activation of X–H Bonds (X = C, N, O) by Nonheme Iron–Oxo Complexes of Variable Basicity

2013 ◽  
Vol 135 (45) ◽  
pp. 17090-17104 ◽  
Author(s):  
Dandamudi Usharani ◽  
David C. Lacy ◽  
A. S. Borovik ◽  
Sason Shaik
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Nonheme Iron ◽  
Atom Transfer ◽  
Oxo Complexes ◽  
Proton Coupled Electron Transfer ◽  
Variable Basicity

Proton-Coupled Electron Transfer versus Hydrogen Atom Transfer in Benzyl/Toluene, Methoxyl/Methanol, and Phenoxyl/Phenol Self-Exchange Reactions

2002 ◽  
Vol 124 (37) ◽  
pp. 11142-11147 ◽  
Author(s):  
James M. Mayer ◽  
David A. Hrovat ◽  
Jennie L. Thomas ◽  
Weston Thatcher Borden
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Exchange Reactions ◽  
Proton Coupled Electron Transfer

Atmospheric formation of the NO3 radical from gas-phase reaction of HNO3 acid with the NH2 radical: proton-coupled electron-transfer versus hydrogen atom transfer mechanisms

2014 ◽  
Vol 16 (36) ◽  
pp. 19437-19445 ◽  
Author(s):  
Josep M. Anglada ◽  
Santiago Olivella ◽  
Albert Solé
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Phase Reaction ◽  
Electron Transfer Mechanism ◽  
Proton Coupled Electron Transfer ◽  
No3 Radical ◽  
Transfer Mechanisms ◽  
Atmospheric Formation

The amidogen radical abstracts the hydrogen from nitric acid through a proton coupled electron transfer mechanism rather than by an hydrogen atom transfer process.

scholarly journals The gas phase oxidation of HCOOH by Cl and NH2 radicals. Proton coupled electron transfer versus hydrogen atom transfer

2019 ◽  
Vol 117 (9-12) ◽  
pp. 1430-1441 ◽  
Author(s):  
Josep M. Anglada ◽  
Ramon Crehuet ◽  
Albert Solé
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Gas Phase ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Proton Coupled Electron Transfer ◽  
Phase Oxidation ◽  
Gas Phase Oxidation

The water–boryl radical as a proton-coupled electron transfer reagent for carbon dioxide, formic acid, and formaldehyde — Theoretical approach

2013 ◽  
Vol 91 (2) ◽  
pp. 155-168
Author(s):  
Waled Tantawy ◽  
Ahmed Hashem ◽  
Nabil Yousif ◽  
Eman Flefel
Keyword(s):  
Carbon Dioxide ◽  
Hydrogen Bond ◽  
Electron Transfer ◽  
Hydrogen Atom ◽  
Transfer Process ◽  
Carbonyl Compounds ◽  
Hydrogen Atom Transfer ◽  
Transfer Reactions ◽  
Atom Transfer ◽  
Proton Coupled Electron Transfer

The thermochemistry of the hydrogen atom transfer reactions from the H2O–BX2 radical system (X = H, CH3, NH2, OH, F) to carbon dioxide, formic acid, and (or) formaldehyde, which produce hydroxyformyl, dihydroxymethyl, and hydroxymethyl radicals, respectively, were investigated theoretically at ROMP2/6–311+G(3DF,2P)//UB3LYP/6–31G(D) and UG3(MP2)-RAD levels of theory. Surprisingly, in the cases of a strong Lewis acid (X = H, CH3, F), the spin transfer process from the water–boryl radical to the carbonyl compounds was barrier-free and associated with a dramatic reduction in the B–H bond dissociation energy (BDE) relative to that of isolated water–borane complexes. Examining the coordinates of these reactions revealed that the entire hydrogen atom transfer process is governed by the proton-coupled electron transfer (PCET) mechanism. Hence, the elucidated mechanism has been applied in the cases of weak Lewis acids (X = NH2, OH), and the variation in the accompanied activation energy was attributed to the stereoelectronic effect interplaying in CO2 and HCOOH compared with HCHO. We ascribed the overall mechanism as a SA-induced five-center cyclic PCET, in which the proton transfers across the so-called complexation-induced hydrogen bond (CIHB) channel, while the SOMOB–LUMOC=O′ interaction is responsible for the electron migration process. Owing to previous reports that interrelate the hydrogen-bonding and the rate of proton-coupled electron-transfer reactions, we postulated that “the rate of the PCET reaction is expected to be promoted by the covalency of the hydrogen bond, and any factor that enhances this covalency could be considered an activator of the PCET process.” This postulate could be considered a good rationale for the lack of a barrier associated with the hydrogen atom transfer from the water-boryl radical system to the carbonyl compounds. Light has been shed on the water–boryl radical reagent from the thermodynamic perspective.

Proton–coupled electron transfer versus hydrogen atom transfer: A density functional reactivity theory characterization

2012 ◽  
Vol 988 ◽  
pp. 13-18 ◽  
Author(s):  
Aiguo Zhong ◽  
Canghua Ge ◽  
Huading Liang ◽  
Huajiang Jiang ◽  
Qizhong Zhou
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Density Functional ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Proton Coupled Electron Transfer

Hydrogen atom transfer versus proton coupled electron transfer mechanism of gallic acid with different peroxy radicals

2017 ◽  
Vol 123 (1) ◽  
pp. 215-230 ◽  
Author(s):  
Dejan Milenković ◽  
Jelena Đorović ◽  
Vladimir Petrović ◽  
Edina Avdović ◽  
Zoran Marković
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Gallic Acid ◽  
Hydrogen Atom Transfer ◽  
Transfer Mechanism ◽  
Atom Transfer ◽  
Peroxy Radicals ◽  
Electron Transfer Mechanism ◽  
Proton Coupled Electron Transfer

The Relation between Hydrogen Atom Transfer and Proton-coupled Electron Transfer in Model Systems

2007 ◽  
pp. 503-562 ◽  
Author(s):  
Justin M. Hodgkiss ◽  
Joel Rosenthal ◽  
Daniel G. Nocera
Keyword(s):  
Electron Transfer ◽  
Hydrogen Atom ◽  
Hydrogen Atom Transfer ◽  
Model Systems ◽  
Atom Transfer ◽  
Proton Coupled Electron Transfer
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