MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDE

The cis ¤ trans isomerization reaction of dithietane-1,3-dioxide ( DTDO) has been studied by means of theoretical methods in the framework of molecular orbital theory. The energetics of this reaction was obtained with several basis sets and levels including both polarization and diffuse functions. E...

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Autores principales:	CONTRERAS,J.GUILLERMO, GERLI,LORENA A., HURTADO,S.MARCELA, MADARIAGA,SANDRA T.
Lenguaje:	English
Publicado:	Sociedad Chilena de Química 2004
Materias:	Dithietane dioxide cis/trans isomerization ab initio calculation NMR spectra
Acceso en línea:	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072004000400011
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spelling	oai:scielo:S0717-970720040004000112005-09-13MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDECONTRERAS,J.GUILLERMOGERLI,LORENA A.HURTADO,S.MARCELAMADARIAGA,SANDRA T. Dithietane dioxide cis/trans isomerization ab initio calculation NMR spectra The cis ¤ trans isomerization reaction of dithietane-1,3-dioxide ( DTDO) has been studied by means of theoretical methods in the framework of molecular orbital theory. The energetics of this reaction was obtained with several basis sets and levels including both polarization and diffuse functions. Electronic correlation has been taken into account by applying second-order perturbation Mller-Plesset theory. The thermodynamics indicates that both isomeric forms are in almost the same concentration in the gas phase, whereas in solution in more polar solvents, the cis form becomes more important. The transition state for the cis ¤ trans interconversion reaction has been fully characterized and the activation energy has been calculated to be 47.8 kcal/mol in the gas phase. In general, the solvent, simulated by the PCM model, lowers Ea as its polarity increases, and in DMSO (e = 46.7) Ea goes down by ca. 20 kcal/mol. The calculated ¹H-NMR chemical shifts are consistent with the experimental data. The predicted 17O and 33S-NMR spectra should allow to distinguish between the two conformationsinfo:eu-repo/semantics/openAccessSociedad Chilena de QuímicaJournal of the Chilean Chemical Society v.49 n.4 20042004-12-01text/htmlhttp://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072004000400011en10.4067/S0717-97072004000400011
institution	Scielo Chile
collection	Scielo Chile
language	English
topic	Dithietane dioxide cis/trans isomerization ab initio calculation NMR spectra
spellingShingle	Dithietane dioxide cis/trans isomerization ab initio calculation NMR spectra CONTRERAS,J.GUILLERMO GERLI,LORENA A. HURTADO,S.MARCELA MADARIAGA,SANDRA T. MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDE
description	The cis ¤ trans isomerization reaction of dithietane-1,3-dioxide ( DTDO) has been studied by means of theoretical methods in the framework of molecular orbital theory. The energetics of this reaction was obtained with several basis sets and levels including both polarization and diffuse functions. Electronic correlation has been taken into account by applying second-order perturbation Mller-Plesset theory. The thermodynamics indicates that both isomeric forms are in almost the same concentration in the gas phase, whereas in solution in more polar solvents, the cis form becomes more important. The transition state for the cis ¤ trans interconversion reaction has been fully characterized and the activation energy has been calculated to be 47.8 kcal/mol in the gas phase. In general, the solvent, simulated by the PCM model, lowers Ea as its polarity increases, and in DMSO (e = 46.7) Ea goes down by ca. 20 kcal/mol. The calculated ¹H-NMR chemical shifts are consistent with the experimental data. The predicted 17O and 33S-NMR spectra should allow to distinguish between the two conformations
author	CONTRERAS,J.GUILLERMO GERLI,LORENA A. HURTADO,S.MARCELA MADARIAGA,SANDRA T.
author_facet	CONTRERAS,J.GUILLERMO GERLI,LORENA A. HURTADO,S.MARCELA MADARIAGA,SANDRA T.
author_sort	CONTRERAS,J.GUILLERMO
title	MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDE
title_short	MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDE
title_full	MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDE
title_fullStr	MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDE
title_full_unstemmed	MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDE
title_sort	mechanism of isomerization in dithietane-1,3-dioxide
publisher	Sociedad Chilena de Química
publishDate	2004
url	http://www.scielo.cl/scielo.php?script=sci_arttext&pid=S0717-97072004000400011
work_keys_str_mv	AT contrerasjguillermo mechanismofisomerizationindithietane13dioxide AT gerlilorenaa mechanismofisomerizationindithietane13dioxide AT hurtadosmarcela mechanismofisomerizationindithietane13dioxide AT madariagasandrat mechanismofisomerizationindithietane13dioxide
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MECHANISM OF ISOMERIZATION IN DITHIETANE-1,3-DIOXIDE

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