Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study

Autores
Torrico Vallejos, Sonia; Erben, Mauricio Federico; Ge, Mao Fa; Willner, Helge; Della Vedova, Carlos Omar
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate (MCPOC) has been synthesized and isolated in cryogenic matrices (argon and xenon). FTIR spectroscopy studies on the matrix isolated compound, supported by DFT(B3LYP)/ 6-311++G(d,p) calculations, allow for the identification of two low-energy conformers (I and II) of the molecule, which differ from each other in the orientation of the ester group relative to the oxazole ring. In both these conformers, the ester moiety is in the s-cis configuration (OdCsOsCH3 dihedral: 0°). Conformer II is ca. 3.0 kJ mol-1 higher in energy than form I in the gas phase. Two additional higher energy conformers, III and IV, with relative energies of ca. 30 and 45 kJ mol-1, respectively, were predicted to exist by the calculations, corresponding to structures where the ester group is in an approximately s-trans arrangement. Annealing of the compound isolated in xenon at 60 K led to aggregation and simultaneous reduction of the population of I compared to that of the more polar conformer II. These results suggest the inversion of the order of stability of the two conformers in that matrix, eventually accompanied by a higher trend of conformer I to aggregate. Full assignment of the observed infrared bands to the two experimentally accessible conformers was carried out for the matrix isolated monomeric species. In addition, the infrared spectra of the neat compound in the low-temperature (10 K) amorphous and crystalline phases, as well as the infrared and Raman spectra of the crystal at room temperature were also obtained and assigned.
Fil: Torrico Vallejos, Sonia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Ge, Mao Fa. Chinese Academy of Sciences; República de China
Fil: Willner, Helge. Bergische Universität; Alemania
Fil: Della Vedova, Carlos Omar. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
Materia
CH3OC(O)SX (X= CN and SCN)
conformation
synthesis
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/277883
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/277883
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical StudyTorrico Vallejos, SoniaErben, Mauricio FedericoGe, Mao FaWillner, HelgeDella Vedova, Carlos OmarCH3OC(O)SX (X= CN and SCN)conformationsynthesishttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate (MCPOC) has been synthesized and isolated in cryogenic matrices (argon and xenon). FTIR spectroscopy studies on the matrix isolated compound, supported by DFT(B3LYP)/ 6-311++G(d,p) calculations, allow for the identification of two low-energy conformers (I and II) of the molecule, which differ from each other in the orientation of the ester group relative to the oxazole ring. In both these conformers, the ester moiety is in the s-cis configuration (OdCsOsCH3 dihedral: 0°). Conformer II is ca. 3.0 kJ mol-1 higher in energy than form I in the gas phase. Two additional higher energy conformers, III and IV, with relative energies of ca. 30 and 45 kJ mol-1, respectively, were predicted to exist by the calculations, corresponding to structures where the ester group is in an approximately s-trans arrangement. Annealing of the compound isolated in xenon at 60 K led to aggregation and simultaneous reduction of the population of I compared to that of the more polar conformer II. These results suggest the inversion of the order of stability of the two conformers in that matrix, eventually accompanied by a higher trend of conformer I to aggregate. Full assignment of the observed infrared bands to the two experimentally accessible conformers was carried out for the matrix isolated monomeric species. In addition, the infrared spectra of the neat compound in the low-temperature (10 K) amorphous and crystalline phases, as well as the infrared and Raman spectra of the crystal at room temperature were also obtained and assigned.Fil: Torrico Vallejos, Sonia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; ArgentinaFil: Ge, Mao Fa. Chinese Academy of Sciences; República de ChinaFil: Willner, Helge. Bergische Universität; AlemaniaFil: Della Vedova, Carlos Omar. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; ArgentinaAmerican Chemical Society2010-05info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/277883Torrico Vallejos, Sonia; Erben, Mauricio Federico; Ge, Mao Fa; Willner, Helge; Della Vedova, Carlos Omar; Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study; American Chemical Society; Journal of Physical Chemistry A; 114; 10; 5-2010; 3703-37121089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp912044rinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp912044rinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-12-23T14:07:22Zoai:ri.conicet.gov.ar:11336/277883instacron:CONICETInstitucionalhttp://ri.conicet.gov.ar/Organismo científico-tecnológicoNo correspondehttp://ri.conicet.gov.ar/oai/requestdasensio@conicet.gov.ar; lcarlino@conicet.gov.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:34982025-12-23 14:07:23.187CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
title Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
spellingShingle Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
Torrico Vallejos, Sonia
CH3OC(O)SX (X= CN and SCN)
conformation
synthesis
title_short Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
title_full Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
title_fullStr Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
title_full_unstemmed Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
title_sort Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study
dc.creator.none.fl_str_mv Torrico Vallejos, Sonia
Erben, Mauricio Federico
Ge, Mao Fa
Willner, Helge
Della Vedova, Carlos Omar
author Torrico Vallejos, Sonia
author_facet Torrico Vallejos, Sonia
Erben, Mauricio Federico
Ge, Mao Fa
Willner, Helge
Della Vedova, Carlos Omar
author_role author
author2 Erben, Mauricio Federico
Ge, Mao Fa
Willner, Helge
Della Vedova, Carlos Omar
author2_role author
author
author
author
dc.subject.none.fl_str_mv CH3OC(O)SX (X= CN and SCN)
conformation
synthesis
topic CH3OC(O)SX (X= CN and SCN)
conformation
synthesis
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate (MCPOC) has been synthesized and isolated in cryogenic matrices (argon and xenon). FTIR spectroscopy studies on the matrix isolated compound, supported by DFT(B3LYP)/ 6-311++G(d,p) calculations, allow for the identification of two low-energy conformers (I and II) of the molecule, which differ from each other in the orientation of the ester group relative to the oxazole ring. In both these conformers, the ester moiety is in the s-cis configuration (OdCsOsCH3 dihedral: 0°). Conformer II is ca. 3.0 kJ mol-1 higher in energy than form I in the gas phase. Two additional higher energy conformers, III and IV, with relative energies of ca. 30 and 45 kJ mol-1, respectively, were predicted to exist by the calculations, corresponding to structures where the ester group is in an approximately s-trans arrangement. Annealing of the compound isolated in xenon at 60 K led to aggregation and simultaneous reduction of the population of I compared to that of the more polar conformer II. These results suggest the inversion of the order of stability of the two conformers in that matrix, eventually accompanied by a higher trend of conformer I to aggregate. Full assignment of the observed infrared bands to the two experimentally accessible conformers was carried out for the matrix isolated monomeric species. In addition, the infrared spectra of the neat compound in the low-temperature (10 K) amorphous and crystalline phases, as well as the infrared and Raman spectra of the crystal at room temperature were also obtained and assigned.
Fil: Torrico Vallejos, Sonia. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Erben, Mauricio Federico. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Química Inorgánica "Dr. Pedro J. Aymonino". Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Química Inorgánica "Dr. Pedro J. Aymonino"; Argentina
Fil: Ge, Mao Fa. Chinese Academy of Sciences; República de China
Fil: Willner, Helge. Bergische Universität; Alemania
Fil: Della Vedova, Carlos Omar. Provincia de Buenos Aires. Gobernación. Comisión de Investigaciones Científicas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - La Plata. Centro de Investigación y Desarrollo en Criotecnología de Alimentos. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Centro de Investigación y Desarrollo en Criotecnología de Alimentos; Argentina
description Methyl 4-chloro-5-phenyl-1,3-oxazole-2-carboxylate (MCPOC) has been synthesized and isolated in cryogenic matrices (argon and xenon). FTIR spectroscopy studies on the matrix isolated compound, supported by DFT(B3LYP)/ 6-311++G(d,p) calculations, allow for the identification of two low-energy conformers (I and II) of the molecule, which differ from each other in the orientation of the ester group relative to the oxazole ring. In both these conformers, the ester moiety is in the s-cis configuration (OdCsOsCH3 dihedral: 0°). Conformer II is ca. 3.0 kJ mol-1 higher in energy than form I in the gas phase. Two additional higher energy conformers, III and IV, with relative energies of ca. 30 and 45 kJ mol-1, respectively, were predicted to exist by the calculations, corresponding to structures where the ester group is in an approximately s-trans arrangement. Annealing of the compound isolated in xenon at 60 K led to aggregation and simultaneous reduction of the population of I compared to that of the more polar conformer II. These results suggest the inversion of the order of stability of the two conformers in that matrix, eventually accompanied by a higher trend of conformer I to aggregate. Full assignment of the observed infrared bands to the two experimentally accessible conformers was carried out for the matrix isolated monomeric species. In addition, the infrared spectra of the neat compound in the low-temperature (10 K) amorphous and crystalline phases, as well as the infrared and Raman spectra of the crystal at room temperature were also obtained and assigned.
publishDate 2010
dc.date.none.fl_str_mv 2010-05
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
http://purl.org/coar/resource_type/c_6501
info:ar-repo/semantics/articulo
format article
status_str publishedVersion
dc.identifier.none.fl_str_mv http://hdl.handle.net/11336/277883
Torrico Vallejos, Sonia; Erben, Mauricio Federico; Ge, Mao Fa; Willner, Helge; Della Vedova, Carlos Omar; Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study; American Chemical Society; Journal of Physical Chemistry A; 114; 10; 5-2010; 3703-3712
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/277883
identifier_str_mv Torrico Vallejos, Sonia; Erben, Mauricio Federico; Ge, Mao Fa; Willner, Helge; Della Vedova, Carlos Omar; Conformational Behavior of CH 3 OC(O)SX (X = CN and SCN) Pseudohalide Congeners. A Combined Experimental and Theoretical Study; American Chemical Society; Journal of Physical Chemistry A; 114; 10; 5-2010; 3703-3712
1089-5639
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp912044r
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp912044r
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by-nc-sa/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
application/pdf
application/pdf
dc.publisher.none.fl_str_mv American Chemical Society
publisher.none.fl_str_mv American Chemical Society
dc.source.none.fl_str_mv reponame:CONICET Digital (CONICET)
instname:Consejo Nacional de Investigaciones Científicas y Técnicas
reponame_str CONICET Digital (CONICET)
collection CONICET Digital (CONICET)
instname_str Consejo Nacional de Investigaciones Científicas y Técnicas
repository.name.fl_str_mv CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicas
repository.mail.fl_str_mv dasensio@conicet.gov.ar; lcarlino@conicet.gov.ar
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score 12.952241

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