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

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F21%3A00545682" target="_blank" >RIV/61388955:_____/21:00545682 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/21:00543194

Výsledek na webu

<a href="http://hdl.handle.net/11104/0322353" target="_blank" >http://hdl.handle.net/11104/0322353</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/celc.202100372" target="_blank" >10.1002/celc.202100372</a>

Jazyk výsledku

angličtina

Název v původním jazyce

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

Popis výsledku v původním jazyce

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.

Název v anglickém jazyce

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

Popis výsledku anglicky

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.

Druh

J_imp - Článek v periodiku v databázi Web of Science

CEP obor

—

OECD FORD obor

10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Projekt

Výsledek vznikl pri realizaci vícero projektů. Více informací v záložce Projekty.

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2021

Kód důvěrnosti údajů

S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

Název periodika

ChemElectroChem

ISSN

2196-0216

e-ISSN

2196-0216

Svazek periodika

8

Číslo periodika v rámci svazku

17

Stát vydavatele periodika

DE - Spolková republika Německo

Počet stran výsledku

7

Strana od-do

3243-3249

Kód UT WoS článku

000655723400001

EID výsledku v databázi Scopus

2-s2.0-85106600032