Proton-Coupled Electron Transfer and the “Linear Approximation” for Coupling to the Donor–Acceptor Distance Fluctuations

2017 ◽  
Vol 121 (10) ◽  
pp. 2199-2207 ◽  
Author(s):  
Bridget Salna ◽  
Abdelkrim Benabbas ◽  
Paul M. Champion
Keyword(s):  
Electron Transfer ◽  
Linear Approximation ◽  
Proton Coupled Electron Transfer ◽  
Donor Acceptor

Guanidines as Reagents in Proton-Coupled Electron-Transfer Reactions and Redox Catalysts

Synlett ◽  
2018 ◽  
Vol 29 (15) ◽  
pp. 1957-1977 ◽  
Author(s):  
Hans-Jörg Himmel
Keyword(s):  
Electron Transfer ◽  
Transfer Reactions ◽  
Redox Activity ◽  
Coupling Reactions ◽  
Proton Coupled Electron Transfer ◽  
Redox Catalysts ◽  
Dehydrogenative Coupling ◽  
Redox Active ◽  
Organic Electron ◽  
Donor Acceptor

Redox-active guanidines are ideal proton-coupled electron-transfer (PCET) reagents, since they combine a high Brønsted basicity with a low and tunable redox potential. In this article, the development of redox-active guanidines (especially guanidino-functionalized aromatics, GFAs) in the last ten years is summarized, and their properties compared to other organic Brønsted bases and organic electron donors. First, some applications in organic chemistry that purely use the redox activity (formation of organic donor–acceptor materials and photochemical reductive C–C coupling reactions) are presented. Then, reactions that involve both proton and electron transfer are reviewed. In stoichiometric reactions, redox-active guanidines are used for the dehydrogenative coupling of thiols and phosphanes. The first redox catalytic applications are discussed, using dioxygen as green oxidizing reagent.1 Introduction2 Redox-Active Amines and Guanidines3 Brønsted Basicity of Amines and Guanidines4 Variations of GFA Compounds5 GFA Compounds in Organic Donor–Acceptor Materials and as Reducing Reagents in Organic Synthesis6 Stoichiometric Dehydrogenative Coupling Reactions with Redox-Active Guanidines7 Guanidines as Redox Catalysts8 Conclusions and Outlook

Amidinium–carboxylate salt bridge mediated proton-coupled electron transfer in a donor–acceptor supramolecular system

2019 ◽  
Vol 6 (5) ◽  
pp. 584-590
Author(s):  
Xiaolei Ren ◽  
Xiaohua Wang ◽  
Yuren Sun ◽  
Xiaodong Chi ◽  
Daniel Mangel ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Salt Bridge ◽  
Supramolecular Polymer ◽  
Supramolecular System ◽  
Salt Bridges ◽  
Proton Coupled Electron Transfer ◽  
System P ◽  
Donor Acceptor

A supramolecular polymer that allows for intrapolymer proton-coupled photoinduced electron transfer was constructed by means of amidinium-carboxylate salt bridges.

Anthracene-based azo dyes for photo-induced proton-coupled electron transfer

2019 ◽  
Vol 55 (42) ◽  
pp. 5874-5877 ◽  
Author(s):  
Amanda N. Oldacre ◽  
Craig A. Pointer ◽  
Shea M. Martin ◽  
Amanda Kemmerer ◽  
Elizabeth R. Young
Keyword(s):  
Electron Transfer ◽  
Azo Dyes ◽  
Proton Coupled Electron Transfer ◽  
Donor Acceptor

Herein, we report a new donor–acceptor system for photo-induced proton-coupled electron transfer (PCET) that leverages an azo linkage as the proton-sensitive component and anthracene as a photo-trigger.

scholarly journals Proton-coupled electron transfer reactions: analytical rate constants and case study of kinetic isotope effects in lipoxygenase

2016 ◽  
Vol 195 ◽  
pp. 171-189 ◽  
Author(s):  
Alexander V. Soudackov ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Rate Constant ◽  
Isotope Effects ◽  
Thermal Fluctuations ◽  
Proton Donor ◽  
Nonadiabatic Transitions ◽  
Proton Coupled Electron Transfer ◽  
Wide Range ◽  
Donor Acceptor ◽  
Vibronic States

A general theory has been developed for proton-coupled electron transfer (PCET), which is vital to a wide range of chemical and biological processes. This theory describes PCET reactions in terms of nonadiabatic transitions between reactant and product electron–proton vibronic states and includes the effects of thermal fluctuations of the solvent or protein environment, as well as the proton donor–acceptor motion. Within the framework of this general PCET theory, a series of analytical rate constant expressions has been derived for PCET reactions in well-defined regimes. Herein, the application of this theory to PCET in the enzyme soybean lipoxygenase illustrates the regimes of validity for the various rate constant expressions and elucidates the fundamental physical principles dictating PCET reactions. Such theoretical studies provide significant physical insights that guide the interpretation of experimental data and lead to experimentally testable predictions. A combination of theoretical treatments with atomic-level simulations is essential to understanding PCET.

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