Comproportionation and Michael addition reactions of electrochemically generated N,N,N’,N’-tetramethyl-1,4-phenylenediamine dication. Synthesis of new unsymmetrical aryl sulfones containing N,N,N’,N’-tetramethyl-1,4-phenylenediamine moiety

Nematollahi, Davood; Hosseinzadeh, Saber; Dadpou, Bita

doi:10.1016/j.jelechem.2015.11.006

Cited by 9 publications

(3 citation statements)

References 30 publications

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“…The abbreviation of this mechanism is a “surface CrevEC’ ” (“rev” stands for reversible) or simply “surface CEC’ mechanism”. This mechanism has not been considered theoretically so far in the literature under voltammetric conditions, although one finds several experimental works related to this mechanism . Commonly, this mechanism is met by surface redox reactions of many coordinative complexes, whose dissociation provides starting material for the electrochemical reaction.…”

Section: Introductionsupporting

confidence: 54%

Theoretical Aspects of a Surface Electrode Reaction Coupled with Preceding and Regenerative Chemical Steps: Square‐wave Voltammetry of a Surface CEC’ Mechanism

Kokoškarova

Gulaboski

2019

Electroanalysis

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Large number of lipophilic substances, whose electrochemical transformation takes place from adsorbed state, belong to the class of so‐called “surface‐redox reactions”. Of these, especially important are the enzymatic redox reactions. With the technique named “protein‐film voltammetry” we can get insight into the chemical features of many lipophilic redox enzymes. Electrochemical processes of many redox adsorbates, occurring at a surface of working electrode, are very often coupled with chemical reactions. In this work, we focus on the application of square‐wave voltammetry (SWV) to study the theoretical features of a surface electrode reaction coupled with two chemical steps. The starting electroactive form Ox(ads) in this mechanism gets initially generated via preceding chemical reaction. After undergoing redox transformation at the working electrode, Ox(ads) species got additionally regenerated via chemical reaction of electrochemically generated product Red(ads) with a given substrate Y. The theory of this so‐called surface CEC’ mechanism is presented for the first time under conditions of square‐wave voltammetry. While we present plenty of calculated voltammograms of this complex electrode mechanism, we focus on the effect of rate of regenerative (catalytic) step to simulated voltammograms. We consider both, electrochemical reactions featuring moderate and fast electron transfer. The obtained voltammetric patterns are very specific, having sometime hybrid‐like features of voltammograms as typical for CE, EC and EC’ mechanisms. We give diagnostic criteria to recognize this complex mechanism in SWV, but we also present hints to access the kinetic and thermodynamic parameters relevant to both chemical steps, and the electrochemical reaction, too. Indeed, the results presented in this work can help experimentalists to design proper experiments to study chemical features of important lipophilic systems.

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Section: Introductionsupporting

confidence: 54%

Theoretical Aspects of a Surface Electrode Reaction Coupled with Preceding and Regenerative Chemical Steps: Square‐wave Voltammetry of a Surface CEC’ Mechanism

Kokoškarova

Gulaboski

2019

Electroanalysis

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“…Based on our experience in the electrochemical generation of quinone diimine [49][50][51] along with the electrochemical and spectroscopic data of the final product, we propose the following mechanism for the electrochemical oxidation of FVB in the presence of 1 (Scheme 1, Part II). In the proposed mechanism, for simplification, the protonation of species is omitted.…”

Section: Resultsmentioning

confidence: 99%

Unsymmetrical Diaryl Sulfones through Electrochemical Oxidation of Fast Violet B in the Presence of Aryl Sulfinic Acids

Jamshidi

Nematollahi

Bayat

et al. 2016

J. Electrochem. Soc.

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Some new unsymmetrical diaryl sulfones were synthesized by anodic oxidation of fast violet B in aqueous/ethanol solutions in the presence of arylsulfinic acids at a carbon electrode. The data show that the electrogenerated N-acetyl-p-benzoquinone diimine was converted to the unsymmetrical diaryl sulfones by Michael type addition reaction with aryl sulfinic acids. This work has led to the development of a high yield, green, reagentless and facile electrochemical method for the synthesis of the described sulfones. In addition, four possible products were optimized at the BP86/def2-SVP level of theory by the parameters, natural charge, LUMO coefficient of Michael acceptor, thermodynamic and kinetic stability.

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“…This is an important detail because when smaller volumes of highly concentrated ferricyanide were added they could rapidly generate local pockets of the twoelectron-oxidized TMPD 2+ species before the reaction mixtures could be stirred. TMPD 2+ is unstable, 35 and solutions prepared by addition of concentrated ferricyanide aliquots gave poorly reproducible results.…”

Section: ■ Materials and Methodsmentioning

confidence: 99%

A Kinetic Investigation of the Early Steps in Cytochrome c Nitrite Reductase (ccNiR)-Catalyzed Reduction of Nitrite

et al. 2021

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The decaheme enzyme cytochrome c nitrite reductase (ccNiR) catalyzes reduction of nitrite to ammonium in a six-electron, eight-proton process. With a strong reductant as the electron source, ammonium is the sole product. However, intermediates accumulate when weaker reductants are employed, facilitating study of the ccNiR mechanism. Herein, the early stages of Shewanella oneidensis ccNiR-catalyzed nitrite reduction were investigated by using the weak reductants N,N,N′,N'-tetramethyl-pphenylenediamine (TMPD) and ferrocyanide. In stopped-flow experiments, reduction of nitrite-loaded ccNiR by TMPD generated

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Comproportionation and Michael addition reactions of electrochemically generated N,N,N’,N’-tetramethyl-1,4-phenylenediamine dication. Synthesis of new unsymmetrical aryl sulfones containing N,N,N’,N’-tetramethyl-1,4-phenylenediamine moiety

Cited by 9 publications

References 30 publications

Theoretical Aspects of a Surface Electrode Reaction Coupled with Preceding and Regenerative Chemical Steps: Square‐wave Voltammetry of a Surface CEC’ Mechanism

Theoretical Aspects of a Surface Electrode Reaction Coupled with Preceding and Regenerative Chemical Steps: Square‐wave Voltammetry of a Surface CEC’ Mechanism

Unsymmetrical Diaryl Sulfones through Electrochemical Oxidation of Fast Violet B in the Presence of Aryl Sulfinic Acids

A Kinetic Investigation of the Early Steps in Cytochrome c Nitrite Reductase (ccNiR)-Catalyzed Reduction of Nitrite

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