Organo‐Mediator Enabled Electrochemical Deuteration of Styrenes

Angewandte Chemie International Edition, Год журнала: 2023, Номер 62(45)

Опубликована: Сен. 12, 2023

Despite widespread use of the deuterium isotope effect, selective labeling chemical molecules remains a major challenge. Herein, facile and general electrochemically driven, organic mediator enabled deuteration styrenes with oxide (D2 O) as economical source was reported. Importantly, this transformation could be suitable for various electron rich mediated by triphenylphosphine (TPP). The reaction proceeded under mild conditions without transition-metal catalysts, affording desired products in good yields excellent D-incorporation (D-inc, up to >99 %). Mechanistic investigations means experiments cyclic voltammetry tests provided sufficient support transformation. Notably, method proved powerful tool late-stage biorelevant compounds.

Язык: Английский

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Electroreductive deuteroarylation of alkenes enabled by an organo-mediator

Chemical Science, Год журнала: 2024, Номер 15(29), С. 11418 - 11427

Опубликована: Янв. 1, 2024

An environmentally friendly electroreduction approach is disclosed for site-specific introduction of deuterium via anti-Markovnikov selective deuteroarylation alkenes and aryl iodides with bipyridine as a mediator D 2 O ‘D’ source.

Язык: Английский

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Design of Cr-Based Molecular Electrocatalyst Systems for the CO₂ Reduction Reaction

Accounts of Chemical Research, Год журнала: 2024, Номер 57(16), С. 2326 - 2335

Опубликована: Авг. 6, 2024

ConspectusHuman influence on the climate system was recently summarized by sixth Intergovernmental Panel Climate Change (IPCC) Assessment Report, which noted that global surface temperatures have increased more rapidly in last 50 years than any other 50-year period 2000 years. Elevated had detrimental impacts, including frequent and intense extreme weather patterns like flooding, wildfires, droughts. In order to limit greenhouse gas emissions, various change policies, emissions trading schemes carbon taxes, been implemented many countries. The most prevalent anthropogenic emitted is dioxide (CO2), accounted for 80% of all U.S. 2022. reduction CO2 through use homogeneous electrocatalysts generally follows a two-electron/two-proton pathway produce either monoxide (CO) with water (H2O) as coproduct or formic acid (HCOOH). These reduced species are relevant industrial applications: Fischer-Tropsch process uses CO H2 fuels commodity chemicals, while HCOOH an energy dense carrier fuel cells useful synthetic reagent. Electrochemically reducing value-added products potential way address its steadily increasing atmospheric concentrations supplanting nonrenewable petrochemical reserves generation new carbon-based resources. selective electrochemical (CO2RR) catalyst systems initially achieved late (and sometimes costly) transition metal active sites, leading field conclude complexes based metals earlier periodic table, chromium (Cr), were nonprivileged CO2RR. However, early table sufficient power mediate CO2RR therefore could be correct coordination environment. This Account describes our efforts develop optimize novel Cr-based redox-active ligand modification strategies redox mediators (RMs). RMs molecules can participate cocatalytically during reaction, transferring electrons─often accompanied protons─to catalytic site. Through mechanistic computational work, we found ligand-based activity key controlling intrinsic selectivity these Cr compounds activation. Ligand-based also essential developing cocatalytic systems, since it enables through-space interactions containing planar aromatic groups, allowing charge transfer occur within assembly. Following summary offer perspective possibilities future development small molecule

Язык: Английский

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Insight into the Role of Entropy in Promoting Electrochemical CO₂ Reduction by Imidazolium Cations

Journal of the American Chemical Society, Год журнала: 2023, Номер 145(50), С. 27657 - 27663

Опубликована: Ноя. 29, 2023

The electroreduction of CO2 plays an important role in achieving a net-zero carbon economy. Imidazolium cations can be used to enhance the rate reduction reactions, but origin this promotion remains poorly understood. In work, we show that presence 1-ethyl-3-methylimidazolium (EMIM+), on Ag electrodes occurs with apparent activation energy near zero, while applied potential influences through pre-exponential factor. Our findings suggest is controlled by initial state entropy, which depends organization at electrochemical interface. Further characterization shows C2-proton EMIM+ consumed during reaction, leading collapse cation and decrease catalytic performance. results have implications for understanding effect reaction rates, as they indicate common picture based vibrational electron transfer reactions insufficient describing impact complex systems, such imidazolium cations.

Язык: Английский

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Catalytic, Spectroscopic, and Theoretical Studies of Fe₄S₄-Based Coordination Polymers as Heterogenous Coupled Proton–Electron Transfer Mediators for Electrocatalysis

Journal of the American Chemical Society, Год журнала: 2024, Номер 146(17), С. 12243 - 12252

Опубликована: Апрель 23, 2024

Iron-sulfur clusters play essential roles in biological systems, and thus synthetic [Fe

Язык: Английский

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Electrochemically enabled (3+2) cycloaddition of unbiased alkenes and β-dicarbonyls

Chemical Communications, Год журнала: 2024, Номер 60(45), С. 5836 - 5839

Опубликована: Янв. 1, 2024

A fluorinated porous carbon electrode and Co-salen catalyst reveal (3+2) cycloaddition of unbiased alkenes β -dicarbonyls to get inaccessible dihydrofurans. It requires no stabilizing group works for both cyclic acyclic -dicarbonyls.

Язык: Английский

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Revealing the Mechanistic Features of an Electrosynthetic Catalytic Reaction and the Role of Redox Mediators through DFT Calculations and Microkinetic Modeling

ChemPhysChem, Год журнала: 2024, Номер 25(15)

Опубликована: Май 13, 2024

Organic electrosynthesis is an emerging field that provides original selectivity while adding features of atom economy, sustainability, and selectivity. Electrosynthesis often enhanced by redox mediators or electroauxiliaries. The mechanistic understanding organic however limited the low lifetime intermediates its difficult detection. In this work, we report a computational analysis mechanism appealing reaction previously reported Mei co-workers which catalyzed copper employs iodide as mediator. Our scheme combines DFT calculations with microkinetic modeling covers both in solution electrodic steps. A detailed obtained reproduces well experimental data opens perspectives for general treatment these processes.

Язык: Английский

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Molecular catalyst and co-catalyst systems based on transition metal complexes for the electrochemical oxidation of alcohols

Chemical Communications, Год журнала: 2025, Номер unknown

Опубликована: Янв. 1, 2025

Selected molecular catalyst systems for electrochemical alcohol oxidation are highlighted, including co-catalyst with redox mediators. Structural and activity trends examined, a focus on future system development principles.

Язык: Английский

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Gold Decorated Amino Silicate Functionalized Titanium Dioxide for Enzymeless Electrochemical Determination of Hydrogen Peroxide

Physica B Condensed Matter, Год журнала: 2025, Номер 714, С. 417431 - 417431

Опубликована: Май 27, 2025

Язык: Английский

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Comparisons of bpy and phen Ligand Backbones in Cr-Mediated (Co-)Electrocatalytic CO₂ Reduction

Organometallics, Год журнала: 2023, Номер 42(11), С. 1139 - 1148

Опубликована: Март 1, 2023

Due to the rise in atmospheric carbon dioxide (CO2) concentrations, there is a need for development of new strategies enhance selectivity and activity electrocatalytic conversion CO2 value-added products. The incorporation redox mediators (RMs) as cocatalysts transfer equivalents during catalysis has been gaining more attention recent years across variety small molecule transformations. We have shown that using Cr-centered complexes with sulfone-based RMs leads an enhancement reduction electrocatalysis under protic conditions via inner-sphere mechanism. In these cocatalytic systems, oxygen atom reduced RM binds Cr center form key intermediate stabilized by pancake bonding between aromatic components catalyst ligand backbone RM. This interaction facilitates electron accesses kinetically favorable reaction pathway. Here, we show expanding character well can cause greater coelectrocatalytic activity. These results suggest further improvements be achieved focusing on kinetic thermodynamic parameters which control association

Язык: Английский

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