Photo-induced proton coupled electron transfer from a benzophenone ‘antenna’ to an isoindoline nitroxide

RSC Advances ◽  
2015 ◽  
Vol 5 (116) ◽  
pp. 95598-95603 ◽  
Author(s):  
Jason C. Morris ◽  
Liam A. Walsh ◽  
Brunell A. Gomes ◽  
Didier Gigmes ◽  
Kathryn E. Fairfull-Smith ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Energy Transfer ◽  
Excited State ◽  
Hydrogen Atom ◽  
Transfer Process ◽  
Energy Transfer Process ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Proton Coupled Electron Transfer

When exposed to light, a novel nitroxide-benzophenone hybrid will undergo an energy transfer process whereby the nitroxide enters an excited state which induces an efficient hydrogen atom transfer from unactivated alkanes.

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.

scholarly journals Evaluation of excited state bond weakening for ammonia synthesis from a manganese nitride: stepwise proton coupled electron transfer is preferred over hydrogen atom transfer

2019 ◽  
Vol 55 (39) ◽  
pp. 5595-5598 ◽  
Author(s):  
Florian Loose ◽  
Dian Wang ◽  
Lei Tian ◽  
Gregory D. Scholes ◽  
Robert R. Knowles ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Excited State ◽  
Hydrogen Atom ◽  
Visible Light ◽  
Driving Force ◽  
Ammonia Synthesis ◽  
Hydrogen Atom Transfer ◽  
Atom Transfer ◽  
Proton Coupled Electron Transfer ◽  
Manganese Nitride

Concepts for the thermodynamically challenging synthesis of weak N–H bonds by photoinduced proton coupled electron transfer are explored. By harvesting visible light as driving force, ammonia synthesis was achieved and mechanistically elucidated.

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.

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