Regularities of the conformations on a single bond; sulfonic esters and sulfonyl derivatives

Kód výsledku v IS VaVaI

<a href="https://www.isvavai.cz/riv?ss=detail&h=RIV%2F60461373%3A22310%2F08%3A00020416" target="_blank" >RIV/60461373:22310/08:00020416 - 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

Regularities of the conformations on a single bond; sulfonic esters and sulfonyl derivatives

Popis výsledku v původním jazyce

The so-called gauche rule preferring the less symmetrical sc conformations on sp3-sp3 bonds was revised by theoretical calculations of five sulfonyl derivatives: C6HSSO2OCH3, CH3SO2OC6H5, ClSO2OC6H5, C6H5SO2CH2Cl and C6HSSO2SO2C6H5. At the same time thelimiting possibilities of common theoretical models were tested in predicting exact geometry and minute energy differences between rotamers. With a larger basis set, for instance at the level B3LYP/ 6-311 + G(3df,3pd)//B3LYP/6-311 + G(3df,3pd) or MP2/6-311 + G(2df,2pd)//MP2/ 6-311+ G(2df,2pd) different methods yielded concordant values of the dihedral angle T characterizing the conformation. However, the predicted values of energy were not in sufficient agreement to give reliable population of rotamers.Probably the best estimate of this population can be obtained by combining the calculated angle T with some experimental quantities, for instance with dipole moments. According to these results, the gauche rule is not a generally valid l

Název v anglickém jazyce

Regularities of the conformations on a single bond; sulfonic esters and sulfonyl derivatives

Popis výsledku anglicky

The so-called gauche rule preferring the less symmetrical sc conformations on sp3-sp3 bonds was revised by theoretical calculations of five sulfonyl derivatives: C6HSSO2OCH3, CH3SO2OC6H5, ClSO2OC6H5, C6H5SO2CH2Cl and C6HSSO2SO2C6H5. At the same time thelimiting possibilities of common theoretical models were tested in predicting exact geometry and minute energy differences between rotamers. With a larger basis set, for instance at the level B3LYP/ 6-311 + G(3df,3pd)//B3LYP/6-311 + G(3df,3pd) or MP2/6-311 + G(2df,2pd)//MP2/ 6-311+ G(2df,2pd) different methods yielded concordant values of the dihedral angle T characterizing the conformation. However, the predicted values of energy were not in sufficient agreement to give reliable population of rotamers.Probably the best estimate of this population can be obtained by combining the calculated angle T with some experimental quantities, for instance with dipole moments. According to these results, the gauche rule is not a generally valid l

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

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Návaznosti

Z - Vyzkumny zamer (s odkazem do CEZ)

Rok uplatnění

2008

Kód důvěrnosti údajů

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

Název periodika

New Journal of Chemistry

ISSN

1144-0546

e-ISSN

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Svazek periodika

32

Číslo periodika v rámci svazku

4

Stát vydavatele periodika

GB - Spojené království Velké Británie a Severního Irska

Počet stran výsledku

5

Strana od-do

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Kód UT WoS článku

000254634300007

EID výsledku v databázi Scopus

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