Electrochemical Cleavage of Carbon-Chlorine Bonds in Multiply Bridge-Chlorinated Bicyclo[1.1.1]pentane-1,3-dicarboxylic Acids

0543194 - ÚOCHB 2022 RIV DE eng J - Journal Article
Kaleta, Jiří - Hromadová, M. - Pospíšil, Lubomír
Electrochemical Cleavage of Carbon-Chlorine Bonds in Multiply Bridge-Chlorinated Bicyclo[1.1.1]pentane-1,3-dicarboxylic Acids.
ChemElectroChem. Roč. 8, č. 17 (2021), s. 3243-3249. ISSN 2196-0216. E-ISSN 2196-0216
R&D Projects: GA ČR(CZ) GX20-03691X; GA ČR(CZ) GA20-13745S
Institutional support: RVO:61388963
Keywords : bicyclo[1.1.1]pentane-1,3-dicarboxylic acids * C−Cl cleavage * protonation * reduction * voltammetry
OECD category: Organic chemistry
Impact factor: 4.782, year: 2021
Method of publishing: Limited access
https://doi.org/10.1002/celc.202100372

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.
Permanent Link: http://hdl.handle.net/11104/0320465