Elektroredukce aromatických oximů: protonace, absorpce, tvorba iminů a substituční efekty

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F06%3A00016920" target="_blank" >RIV/60461373:22310/06:00016920 - isvavai.cz</a>

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Electroreduction of Aromatic Oximes: Diprotonation, Adsorption, Imine Formation, and Substituent Effect

Popis výsledku v původním jazyce

Aromatic oximes are reduced in aqueous solution in a four-electron process. The reducible species in the pH range 5-8 is a diprotonated form of the oxime. This species is generated in the course of electrolysis in the vicinity of the electrode surface from the adsorbed neutral form of the oxime. The reduction is initiated by a cleavage of the N-O bond. The diprotonation facilitates the reduction process by the preformation of OH2 + as a good leaving group and by a positive charge on the azomethine nitrogen. Diprotonation has been proven based on shapes of i ) f(pH) plots, by observed shifts of half-wave potentials with pH and by comparison with the reduction of nitrones. Some observed deviations from theoretical i ) f(pH) plots were attributed to the role of adsorption on the rate of protonation. Adsorption is also responsible for dips on some of the i-E curves. Adsorption plays a role at concentrations as low as 1 10-5 M, when the electrode surface is still not fully covered. This ind

Název v anglickém jazyce

Electroreduction of Aromatic Oximes: Diprotonation, Adsorption, Imine Formation, and Substituent Effect

Popis výsledku anglicky

Aromatic oximes are reduced in aqueous solution in a four-electron process. The reducible species in the pH range 5-8 is a diprotonated form of the oxime. This species is generated in the course of electrolysis in the vicinity of the electrode surface from the adsorbed neutral form of the oxime. The reduction is initiated by a cleavage of the N-O bond. The diprotonation facilitates the reduction process by the preformation of OH2 + as a good leaving group and by a positive charge on the azomethine nitrogen. Diprotonation has been proven based on shapes of i ) f(pH) plots, by observed shifts of half-wave potentials with pH and by comparison with the reduction of nitrones. Some observed deviations from theoretical i ) f(pH) plots were attributed to the role of adsorption on the rate of protonation. Adsorption is also responsible for dips on some of the i-E curves. Adsorption plays a role at concentrations as low as 1 10-5 M, when the electrode surface is still not fully covered. This ind

Druh

J_x - Nezařazeno - Článek v odborném periodiku (Jimp, Jsc a Jost)

CEP obor

CC - Organická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/GA203%2F01%2F1093" target="_blank" >GA203/01/1093: Vliv elektronové distribuce na reaktivitu oximů vůči esterům</a><br>

Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2006

Kód důvěrnosti údajů

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

Název periodika

JOURNAL OF PHYSICAL CHEMISTRY B

ISSN

1520-6106

e-ISSN

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Svazek periodika

110

Číslo periodika v rámci svazku

3

Stát vydavatele periodika

US - Spojené státy americké

Počet stran výsledku

12

Strana od-do

6785-6796

Kód UT WoS článku

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EID výsledku v databázi Scopus

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