Number of the records: 1
Electrochemical Cleavage of Carbon-Chlorine Bonds in Multiply Bridge-Chlorinated Bicyclo[1.1.1]pentane-1,3-dicarboxylic Acids
- 1.
SYSNO ASEP 0545682 Document Type J - Journal Article R&D Document Type Journal Article Subsidiary J Článek ve WOS Title Electrochemical Cleavage of Carbon-Chlorine Bonds in Multiply Bridge-Chlorinated Bicyclo[1.1.1]pentane-1,3-dicarboxylic Acids Author(s) Kaleta, J. (CZ)
Hromadová, Magdaléna (UFCH-W) RID, ORCID, SAI
Pospíšil, Lubomír (UFCH-W) RID, ORCIDSource Title ChemElectroChem. - : Wiley - ISSN 2196-0216
Roč. 8, č. 17 (2021), s. 3243-3249Number of pages 7 s. Language eng - English Country DE - Germany Keywords potential sweep voltammetry ; volatile organic-compounds ; electron-transfer ; electrocatalytic dechlorination ; activated olefins ; transition ; mechanisms ; reduction ; stepwise ; bicyclo[1.1.1]pentane-1,3-dicarboxylic acids ; reduction ; C-Cl cleavage ; protonation ; voltammetry Subject RIV CG - Electrochemistry OECD category Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis) R&D Projects GX20-03691X GA ČR - Czech Science Foundation (CSF) Method of publishing Limited access Institutional support UFCH-W - RVO:61388955 UT WOS 000655723400001 EID SCOPUS 85106600032 DOI 10.1002/celc.202100372 Annotation Reduction of five derivatives of bicyclo[1.1.1]pentane-1,3-dicarboxylic acid containing one to four chlorine substituents on methylene bridges were investigated by cyclic voltammetry and electrochemical impedance spectroscopy. Electrochemical cleavage of C-Cl bonds and the reduction of H+ provided by dissociation of COOH groups are two competing processes characterized by different time constants. A concerted mechanism of C-Cl bonds cleavage is operative. The location of LUMO orbitals changes with increasing number of chlorine substituents from COOH sites to bicyclo[1.1.1]pentane. Carboxylic groups participate in the protonation of intermediates formed by the C-Cl bond rupture. The esterification of two derivatives eliminates the self-protonation. Esters are reduced only at very negative potentials near the end of an available potential window. Workplace J. Heyrovsky Institute of Physical Chemistry Contact Michaela Knapová, michaela.knapova@jh-inst.cas.cz, Tel.: 266 053 196 Year of Publishing 2022 Electronic address http://hdl.handle.net/11104/0322353
Number of the records: 1