High-Valent Oxo, Methoxorhenium Complexes: Models for Intermediates and Transition States in Proton-Coupled Multi-Electron Transfer Reactions

1995 ◽  
Vol 117 (4) ◽  
pp. 1411-1421 ◽  
Author(s):  
M. S. Ram ◽  
Lisa M. Skeens-Jones ◽  
Christopher S. Johnson ◽  
Xiao Lian Zhang ◽  
Charlotte Stern ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Transition States ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
High Valent

Electron transfer and catalysis with high-valent metal-oxo complexes

2015 ◽  
Vol 44 (15) ◽  
pp. 6696-6705 ◽  
Author(s):  
Shunichi Fukuzumi
Keyword(s):  
Electron Transfer ◽  
Photoinduced Electron Transfer ◽  
Transfer Reactions ◽  
Electron Transfer Reactions ◽  
Oxo Complexes ◽  
High Valent

High-valent metal-oxo complexes are produced by thermal and photoinduced electron-transfer reactions, acting as catalysts for oxygenation of substrates using water or dioxygen as an oxygen source.

scholarly journals Converting the bis-FeIV state of the diheme enzyme MauG to Compound I decreases the reorganization energy for electron transfer

2015 ◽  
Vol 473 (1) ◽  
pp. 67-72
Author(s):  
Brian A. Dow ◽  
Victor L. Davidson
Keyword(s):  
Electron Transfer ◽  
Reorganization Energy ◽  
Transfer Reactions ◽  
Compound I ◽  
Electron Transfer Reactions ◽  
Charge Delocalization ◽  
Redox Center ◽  
High Valent ◽  
Redox Centers

The extent of charge delocalization throughout the diheme redox center of MauG influences the reorganization energy associated with the electron transfer reactions to the high-valent hemes. This explains how enzymes can optimize various reactions by utilizing different high-valent redox centers.

Non-covalent π–π stacking interactions turn off non-adiabatic effects in proton-coupled electron transfer reactions

2017 ◽  
Vol 19 (10) ◽  
pp. 6969-6972 ◽  
Author(s):  
Leonardo Muñoz-Rugeles ◽  
Annia Galano ◽  
J. Raúl Alvarez-Idaboy
Keyword(s):  
Electron Transfer ◽  
Excited States ◽  
Transition States ◽  
Transfer Reactions ◽  
Stacking Interactions ◽  
Electron Transfer Reactions ◽  
Proton Coupled Electron Transfer ◽  
Π Stacking

Stacked transition states correspond to a PCET mechanism, albeit ground and first-excited states are separated by more than 20 kcal mol−1. The latter is usually attributed to HAT.

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