ChemInform Abstract: POLAROGRAPHIC AND COULOMETRIC BEHAVIOR OF AROMATIC NITRO COMPOUNDS‐ PART IV. NITROBENZENE IN ACETONITRILE

Vijayalakshamma, SK; Subrahmanya, R. S.

doi:10.1002/chin.197622053

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“…The electrochemical reduction of nitrobenzene (PhNO 2 ) has been studied in water and aprotic solvents, either in absence or in presence of proton donors. [4][5][6][7][8][9][10][11][12][13] The electrochemical reduction mechanism involves many electron and proton transfer steps, which, depending on the experimental conditions, afford differ-ent reduction products like phenylhydroxylamine (PhNHOH), azoxybenzene (Ph-N + (O À )=NÀ Ph), azobenzene (PhÀ N=NÀ Ph), and aniline (PhNH 2 ) among others. [4,5,14] This kind of compounds keep some analogy with a wider class of products involving N=N and NÀ N bonds, which are of relevance for pharmaceuticals and agrochemicals applications.…”

Section: Introductionmentioning

confidence: 99%

Revisiting the Electrochemical Reduction Mechanism of Nitrosobenzene in Acetonitrile. Concomitant Reactions and Voltammetric Simulation

Palacios‐Ramírez,

González

2024

ChemElectroChem

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The electrochemical reduction mechanism of nitrosobenzene in acetonitrile was reconsidered in this work. The commonly accepted mechanism assumes that the nitrosobenzene radical anion dimerize to yield a dianion, which decompose into azoxybenzene as the reduction product. Even though this proposal is consistent with preparative experiments, it does not reproduce fully the experimental voltammetric behaviour when it is simulated. Also, It does not explain why the apparent electron number is different in the time scale of cyclic voltammetry and preparative electrolysis. To understand these discrepancies, it was proposed the intervention of reactions consuming part of the starting nitrosobenzene, which allowed to reconsider the role of alternative chemical reactions like that occurring between the anion of phenylhydroxylamine with nitrosobenzene and the hydroxyl ion with nitrosobenzene. In this framework, these concomitant reactions were additionally included in the mechanism to simulate the voltammetric behaviour at different scan rates. Thermodynamic and kinetic parameters of the extended mechanism are reported. Since in the hydroxyl ion is either product or reactive in some reaction steps, the global mechanism was deemed to occurs as a kind of loop.

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