Regioselective electrochemical reduction of 2,4-dichlorobiphenyl – Distinct standard reduction potentials for carbon–chlorine bonds using convolution potential sweep voltammetry

Mechanism and Regioselectivity of the Electrochemical Reduction in Polychlorobiphenyls (PCBs): Kinetic Analysis for the Successive Reduction of Chlorines from Dichlorobiphenyls

“…The radical without Cl atom in the ortho position is more stable (see Table 2) because the ortho-Cl elimination removes the ring strain between the two benzene rings in the biphenyl compound as has been demonstrated in an earlier study. 16 This is the reason for ortho selectivity of the reduction process which is also confirmed from the bulk electrolysis result. The gas phase optimized geometry of the anion radical of 2, 3-dichlorobiphenyl is employed.…”

pH dependent kinetic insights of electrocatalytic arsenite oxidation reactions at Pt surface

“…In case of pH 7 and 9, we obtained the values of  as 0.29 (±0.0025) and 0.33(±0.0025). According to literature, an irreversible process occurring with transfer coefficient less than 0.5, proceeds using a concerted mechanism [19,22].Thus diagnosis of the voltammetric data indicates that arsenite ions are oxidized on a Pt surface at pH 7 to 9 using a single step process, where electron transfer and As-O bond formation were concerted to generate arsenate ions.…”

“…The kinetics of an electrochemical process is closely related to diffusion coefficient of the target analyte. Thanks to the convolution potential sweep voltammetry (CPSV) as this is an easy and effective technique for both determining the diffusion coefficient and resolving the kinetics of an electro-active species [19][20][21][22]. In the present study, we have firstly evaluated the pH dependent D values of arsenite ions using CPSV technique and then we exploited these values in determining electro-kinetic parameters of electrocatalytic arsenite oxidation reactions using a Pt disc electrode at room temperature.…”

Cobalt-Catalyzed Methoxycarbonylation of Substituted Dichlorobenzenes as an Example of a Facile Radical Anion Nucleophilic Substitution in Chloroarenes

“…Notably, the transition state TS para which leads to the para C–Cl bond cleavage to give a radical R para is a late TS compared with TS ortho (Figure 2). We obtained similar results by calculating the possible radical anions fragmentation pathways of PCBs, for which the reaction also proceeds by stepwise path III [50,51].…”