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

Result code in 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>

Result on the web

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DOI - Digital Object Identifier

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Result language

angličtina

Original language name

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

Original language description

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

Czech name

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

Czech description

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

Type

J_x - Unclassified - Peer-reviewed scientific article (Jimp, Jsc and Jost)

CEP classification

CC - Organic chemistry

OECD FORD branch

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Project

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Continuities

Z - Vyzkumny zamer (s odkazem do CEZ)

Publication year

2008

Confidentiality

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

Name of the periodical

New Journal of Chemistry

ISSN

1144-0546

e-ISSN

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Volume of the periodical

32

Issue of the periodical within the volume

4

Country of publishing house

GB - UNITED KINGDOM

Number of pages

5

Pages from-to

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UT code for WoS article

000254634300007

EID of the result in the Scopus database

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