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

Result code in 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>
Result on the web
<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>

Result language
angličtina
Original language name
Electrochemical, EPR, and quantum chemical study of reductive cleavage of cone-Calix[4]arene nosylates – New electrosynthetic approach
Original language description
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.
Czech name
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Czech description
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Type
J<sub>imp</sub> - Article in a specialist periodical, which is included in the Web of Science database
CEP classification
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OECD FORD branch
10405 - Electrochemistry (dry cells, batteries, fuel cells, corrosion metals, electrolysis)

Project
<a href="/en/project/GA21-23261S" target="_blank" >GA21-23261S: Interconnected azamacrocyclic complexes – new kind of molecular electronics</a><br>
Continuities
I - Institucionalni podpora na dlouhodoby koncepcni rozvoj vyzkumne organizace

Publication year
2023
Confidentiality
S - Úplné a pravdivé údaje o projektu nepodléhají ochraně podle zvláštních právních předpisů

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