Electrochemical, EPR, and quantum chemical study of reductive cleavage of cone-Calix[4]arene nosylates – New electrosynthetic approach

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F61388955%3A_____%2F23%3A00580136" target="_blank" >RIV/61388955:_____/23:00580136 - isvavai.cz</a>

Výsledek na webu

<a href="https://hdl.handle.net/11104/0348902" target="_blank" >https://hdl.handle.net/11104/0348902</a>

DOI - Digital Object Identifier

<a href="http://dx.doi.org/10.1002/elsa.202100221" target="_blank" >10.1002/elsa.202100221</a>

Jazyk výsledku

angličtina

Název v původním jazyce

Electrochemical, EPR, and quantum chemical study of reductive cleavage of cone-Calix[4]arene nosylates – New electrosynthetic approach

Popis výsledku v původním jazyce

The mechanism of electrochemical reduction of a series of six cone-calix[4]arene-bis-nosylates (4-nitrophenylsulfonate aryl esters) was investigated on mercury electrodes using DC-polarography and cyclic voltammetry (CV) combined with in situ electron paramagnetic resonance (EPR)-spectroelectrochemistry in aprotic dimethylformamide. Model compounds – expected fragments and products - were studied for comparison. The experimental results are supported by quantum chemical calculations. All calix[4]arene-bis-nosylates are reduced in a first reversible step to bis-(radical anion) by two simultaneous one-electron transfers. Each of the two electrons is unpaired and separately localized on two nosylate groups.nIn the second reduction step next 2×2 electrons are transferred and both sulfonate ester groups are cleaved to two 4-nitro-benzenesulfinate ions and a calixarene bis-phenolate (95%). This electroreductive generation of arylsulfinate anions is a significant finding from the electrosynthetic point of view. Activated arylsulfinates, the synthesis of which is generally difficult, can be easily prepared by electrochemical reduction of the nosyl esters.

Název v anglickém jazyce

Electrochemical, EPR, and quantum chemical study of reductive cleavage of cone-Calix[4]arene nosylates – New electrosynthetic approach

Popis výsledku anglicky

The mechanism of electrochemical reduction of a series of six cone-calix[4]arene-bis-nosylates (4-nitrophenylsulfonate aryl esters) was investigated on mercury electrodes using DC-polarography and cyclic voltammetry (CV) combined with in situ electron paramagnetic resonance (EPR)-spectroelectrochemistry in aprotic dimethylformamide. Model compounds – expected fragments and products - were studied for comparison. The experimental results are supported by quantum chemical calculations. All calix[4]arene-bis-nosylates are reduced in a first reversible step to bis-(radical anion) by two simultaneous one-electron transfers. Each of the two electrons is unpaired and separately localized on two nosylate groups.nIn the second reduction step next 2×2 electrons are transferred and both sulfonate ester groups are cleaved to two 4-nitro-benzenesulfinate ions and a calixarene bis-phenolate (95%). This electroreductive generation of arylsulfinate anions is a significant finding from the electrosynthetic point of view. Activated arylsulfinates, the synthesis of which is generally difficult, can be easily prepared by electrochemical reduction of the nosyl esters.

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

<a href="/cs/project/GA21-23261S" target="_blank" >GA21-23261S: Propojené azamakrocyklické komplexy – nový druh molekulární elektroniky</a><br>

Návaznosti

I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Rok uplatnění

2023

Kód důvěrnosti údajů

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

Název periodika

Electrochemical Science Advances

ISSN

2698-5977

e-ISSN

—

Svazek periodika

3

Číslo periodika v rámci svazku

6

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

9

Strana od-do

e2100221

Kód UT WoS článku

001134956600005

EID výsledku v databázi Scopus

2-s2.0-85179183964