A biomimetic phenol substituent effect on the reaction of a dimethylplatinum(ii) complex with oxygen: proton coupled electron transfer and multiple proton relay

2015 ◽  
Vol 51 (51) ◽  
pp. 10334-10336 ◽  
Author(s):  
Mohamed E. Moustafa ◽  
Paul D. Boyle ◽  
Richard J. Puddephatt
Keyword(s):  
Electron Transfer ◽  
Substituent Effect ◽  
Dramatic Effect ◽  
Proton Coupled Electron Transfer ◽  
Proton Relay

A phenol substituent has a dramatic effect on the oxidation of a dimethylplatinum(ii) complex with O2.

Unveiling mechanistic implications of water ‎oxidation reaction boosted by guanidine proton relay: a chemical-electrochemical-chemical pathway and a non-‎concerted proton-electron transfer

2021 ◽  
Author(s):  
Mojtaba Shamsipur ◽  
Moslem - Ardeshiri ◽  
Avat Taherpour ◽  
Afshin Pashabadi
Keyword(s):  
Electron Transfer ◽  
Water Oxidation ◽  
Oxidation Reaction ◽  
Proton Coupled Electron Transfer ◽  
Proton Relay ◽  
Artificial Water

Concerted or non-concerted; these are two competitive pathways that involve in proton-coupled ‎electron transfer-driven artificial water oxidation reaction (WOR). It is known that in the designed metal-based ‎electrocatalysts applied to...

Proton-coupled electron transfer in the reduction of diiron hexacarbonyl complexes and its enhancement on the electrocatalytic reduction of protons by a pendant basic group

2019 ◽  
Vol 48 (36) ◽  
pp. 13711-13718 ◽  
Author(s):  
Wei Zhong ◽  
Li Wu ◽  
Weidong Jiang ◽  
Yulong Li ◽  
Natarajan Mookan ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Electrocatalytic Reduction ◽  
Proton Reduction ◽  
Basic Group ◽  
Proton Coupled Electron Transfer ◽  
Proton Relay ◽  
Kinetic Resistance

The pendant basic groups in a diiron complex acted as proton relay to ease the kinetic resistance in proton reduction and enhance proton-coupled electron transfer (PCET).

scholarly journals Nickel phlorin intermediate formed by proton-coupled electron transfer in hydrogen evolution mechanism

2015 ◽  
Vol 113 (3) ◽  
pp. 485-492 ◽  
Author(s):  
Brian H. Solis ◽  
Andrew G. Maher ◽  
Dilek K. Dogutan ◽  
Daniel G. Nocera ◽  
Sharon Hammes-Schiffer
Keyword(s):  
Electron Transfer ◽  
Proton Transfer ◽  
Hydrogen Evolution ◽  
Density Functional ◽  
Density Functional Theory Calculations ◽  
Strong Acid ◽  
Cyclic Voltammograms ◽  
Intramolecular Electron Transfer ◽  
Proton Coupled Electron Transfer ◽  
Proton Relay

The development of more effective energy conversion processes is critical for global energy sustainability. The design of molecular electrocatalysts for the hydrogen evolution reaction is an important component of these efforts. Proton-coupled electron transfer (PCET) reactions, in which electron transfer is coupled to proton transfer, play an important role in these processes and can be enhanced by incorporating proton relays into the molecular electrocatalysts. Herein nickel porphyrin electrocatalysts with and without an internal proton relay are investigated to elucidate the hydrogen evolution mechanisms and thereby enable the design of more effective catalysts. Density functional theory calculations indicate that electrochemical reduction leads to dearomatization of the porphyrin conjugated system, thereby favoring protonation at the meso carbon of the porphyrin ring to produce a phlorin intermediate. A key step in the proposed mechanisms is a thermodynamically favorable PCET reaction composed of intramolecular electron transfer from the nickel to the porphyrin and proton transfer from a carboxylic acid hanging group or an external acid to the meso carbon of the porphyrin. The C–H bond of the active phlorin acts similarly to the more traditional metal-hydride by reacting with acid to produce H2. Support for the theoretically predicted mechanism is provided by the agreement between simulated and experimental cyclic voltammograms in weak and strong acid and by the detection of a phlorin intermediate through spectroelectrochemical measurements. These results suggest that phlorin species have the potential to perform unique chemistry that could prove useful in designing more effective electrocatalysts.

scholarly journals Electron–Nuclear Dynamics Accompanying Proton-Coupled Electron Transfer

2021 ◽  
Vol 143 (8) ◽  
pp. 3104-3112
Author(s):  
Yusuke Yoneda ◽  
S. Jimena Mora ◽  
James Shee ◽  
Brian L. Wadsworth ◽  
Eric A. Arsenault ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Nuclear Dynamics ◽  
Proton Coupled Electron Transfer

Facile proton-coupled electron transfer enabled by coordination-induced E–H bond weakening to boron

2021 ◽  
Author(s):  
Anthony Wong ◽  
Arunavo Chakraborty ◽  
Deependra Bawari ◽  
Guang Wu ◽  
Roman Dobrovetsky ◽  
...  
Keyword(s):  
Electron Transfer ◽  
Proton Coupled Electron Transfer

Coordination induced bond weakening (CIBW) leads to facile PCET at various E–H bonds.

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