Validity of the Hammett equation for isolated molecules: basicity of 3- and 4-substituted benzonitriles

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F04%3A00011341" target="_blank" >RIV/60461373:22310/04:00011341 - isvavai.cz</a>

Nalezeny alternativní kódy

RIV/61388963:_____/04:00100790

Výsledek na webu

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DOI - Digital Object Identifier

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Jazyk výsledku

angličtina

Název v původním jazyce

Validity of the Hammett equation for isolated molecules: basicity of 3- and 4-substituted benzonitriles

Popis výsledku v původním jazyce

Atomic and electronic energies of 27 3- and 4-substituted benzonitriles and of their protonated forms were calculated within the framework of density functional theory (DFT) at the B3LYP/6-311 + G(d,p) level. The substituent effects were expressed by isodesmic homodesmotic reactions, separately for the molecule of benzonitrile [eqn. (7)], for the protonated form [eqn. (8)] and for the resulting basicity [eqn. (6)]. With several molecules, actual site of protonation may be ambiguous and was determined inmost cases from the energies of both protonated forms. In particular 4-aminobenzonitrile, 3-formylbenzonitrile and both nitrobenzonitriles are protonated on the CN group, while 3-aminobenzonitrile and both dimethylaminobenzonitriles on the substituent.The behaviour of methylsulfonylbenzonitriles is still doubtful. The validity of the Hammett equation was tested by correlation with the energies of equally substituted benzoic acids. It holds within the gradually extended range of validit

Název v anglickém jazyce

Validity of the Hammett equation for isolated molecules: basicity of 3- and 4-substituted benzonitriles

Popis výsledku anglicky

Atomic and electronic energies of 27 3- and 4-substituted benzonitriles and of their protonated forms were calculated within the framework of density functional theory (DFT) at the B3LYP/6-311 + G(d,p) level. The substituent effects were expressed by isodesmic homodesmotic reactions, separately for the molecule of benzonitrile [eqn. (7)], for the protonated form [eqn. (8)] and for the resulting basicity [eqn. (6)]. With several molecules, actual site of protonation may be ambiguous and was determined inmost cases from the energies of both protonated forms. In particular 4-aminobenzonitrile, 3-formylbenzonitrile and both nitrobenzonitriles are protonated on the CN group, while 3-aminobenzonitrile and both dimethylaminobenzonitriles on the substituent.The behaviour of methylsulfonylbenzonitriles is still doubtful. The validity of the Hammett equation was tested by correlation with the energies of equally substituted benzoic acids. It holds within the gradually extended range of validit

Druh

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

CEP obor

CF - Fyzikální chemie a teoretická chemie

OECD FORD obor

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Projekt

<a href="/cs/project/LN00A032" target="_blank" >LN00A032: Struktura a dynamika komplexních molekulových systémů a biomolekul</a><br>

Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2004

Kód důvěrnosti údajů

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

Název periodika

Physical Chemistry Chemical Physics

ISSN

1463-9076

e-ISSN

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Svazek periodika

6

Číslo periodika v rámci svazku

14

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

8

Strana od-do

3864-71

Kód UT WoS článku

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EID výsledku v databázi Scopus

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