Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study

Autores
Erben, Mauricio Federico; Della Vedova, Carlos Omar; Romano, Rosana Mariel; Boese, Roland; Oberhammer, Heinz; Willner, Helge; Sala, Oswaldo
Año de publicación
2002
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The molecular structure and conformational properties of methoxycarbonylsulfenyl chloride, CH3OC(O)SCl, were determinated in the gas and solid phases by gas electron diffraction, low-temperature X-ray diffraction, and vibrational spectroscopy. Furthermore, quantum chemical calculations were performed. Experimental and theoretical methods result in structures with a planar C−O−C(O)−S−Cl skeleton. The electron diffraction intensities are reproduced best with a mixture of 72(8)% syn and 28(8)% anti conformers (S−Cl bond synperiplanar/antiperiplanar with respect to CdO bond) and the O−CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced very well by Hartree−Fock approximation and by density functional theory at different levels of theory but not by the MP2/6-311G* method, which overestimates the value of ∆G° between the syn and anti conformers. The results are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated CH3OC(O)SCl with broad-band UV−visible irradiation produces an interconversion of the conformers, and the concomitant decomposition leads to formation of OCS and CO molecules.
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: Della Vedova, Carlos Omar. 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: Romano, Rosana Mariel. 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: Boese, Roland. Universitat Essen; Alemania
Fil: Oberhammer, Heinz. Eberhard Karls Universität Tübingen; Alemania
Fil: Willner, Helge. Universitat Essen; Alemania
Fil: Sala, Oswaldo. Universidade de Sao Paulo; Brasil
Materia
MOLECULAR STRUCTURE
GAS
ELECTRON DIFFRACTION
LOW-TEMPERATURE X-RAY DIFFRACTION
VIBRATIONAL SPECTROSCOPY
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:11336/186615
Acceder
id CONICETDig_1f25795b5e6cdcd19f76f81b931f2956
oai_identifier_str oai:ri.conicet.gov.ar:11336/186615
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical studyErben, Mauricio FedericoDella Vedova, Carlos OmarRomano, Rosana MarielBoese, RolandOberhammer, HeinzWillner, HelgeSala, OswaldoMOLECULAR STRUCTUREGASELECTRON DIFFRACTIONLOW-TEMPERATURE X-RAY DIFFRACTIONVIBRATIONAL SPECTROSCOPYhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The molecular structure and conformational properties of methoxycarbonylsulfenyl chloride, CH3OC(O)SCl, were determinated in the gas and solid phases by gas electron diffraction, low-temperature X-ray diffraction, and vibrational spectroscopy. Furthermore, quantum chemical calculations were performed. Experimental and theoretical methods result in structures with a planar C−O−C(O)−S−Cl skeleton. The electron diffraction intensities are reproduced best with a mixture of 72(8)% syn and 28(8)% anti conformers (S−Cl bond synperiplanar/antiperiplanar with respect to CdO bond) and the O−CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced very well by Hartree−Fock approximation and by density functional theory at different levels of theory but not by the MP2/6-311G* method, which overestimates the value of ∆G° between the syn and anti conformers. The results are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated CH3OC(O)SCl with broad-band UV−visible irradiation produces an interconversion of the conformers, and the concomitant decomposition leads to formation of OCS and CO molecules.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"; ArgentinaFil: Della Vedova, Carlos Omar. 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: Romano, Rosana Mariel. 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: Boese, Roland. Universitat Essen; AlemaniaFil: Oberhammer, Heinz. Eberhard Karls Universität Tübingen; AlemaniaFil: Willner, Helge. Universitat Essen; AlemaniaFil: Sala, Oswaldo. Universidade de Sao Paulo; BrasilAmerican Chemical Society2002-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/186615Erben, Mauricio Federico; Della Vedova, Carlos Omar; Romano, Rosana Mariel; Boese, Roland; Oberhammer, Heinz; et al.; Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study; American Chemical Society; Inorganic Chemistry; 41; 5; 12-2002; 1064-10710020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic010748yinfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic010748yinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:19:08Zoai:ri.conicet.gov.ar:11336/186615instacron: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:34982025-09-10 13:19:08.707CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
title Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
spellingShingle Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
Erben, Mauricio Federico
MOLECULAR STRUCTURE
GAS
ELECTRON DIFFRACTION
LOW-TEMPERATURE X-RAY DIFFRACTION
VIBRATIONAL SPECTROSCOPY
title_short Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
title_full Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
title_fullStr Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
title_full_unstemmed Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
title_sort Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study
dc.creator.none.fl_str_mv Erben, Mauricio Federico
Della Vedova, Carlos Omar
Romano, Rosana Mariel
Boese, Roland
Oberhammer, Heinz
Willner, Helge
Sala, Oswaldo
author Erben, Mauricio Federico
author_facet Erben, Mauricio Federico
Della Vedova, Carlos Omar
Romano, Rosana Mariel
Boese, Roland
Oberhammer, Heinz
Willner, Helge
Sala, Oswaldo
author_role author
author2 Della Vedova, Carlos Omar
Romano, Rosana Mariel
Boese, Roland
Oberhammer, Heinz
Willner, Helge
Sala, Oswaldo
author2_role author
author
author
author
author
author
dc.subject.none.fl_str_mv MOLECULAR STRUCTURE
GAS
ELECTRON DIFFRACTION
LOW-TEMPERATURE X-RAY DIFFRACTION
VIBRATIONAL SPECTROSCOPY
topic MOLECULAR STRUCTURE
GAS
ELECTRON DIFFRACTION
LOW-TEMPERATURE X-RAY DIFFRACTION
VIBRATIONAL SPECTROSCOPY
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv The molecular structure and conformational properties of methoxycarbonylsulfenyl chloride, CH3OC(O)SCl, were determinated in the gas and solid phases by gas electron diffraction, low-temperature X-ray diffraction, and vibrational spectroscopy. Furthermore, quantum chemical calculations were performed. Experimental and theoretical methods result in structures with a planar C−O−C(O)−S−Cl skeleton. The electron diffraction intensities are reproduced best with a mixture of 72(8)% syn and 28(8)% anti conformers (S−Cl bond synperiplanar/antiperiplanar with respect to CdO bond) and the O−CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced very well by Hartree−Fock approximation and by density functional theory at different levels of theory but not by the MP2/6-311G* method, which overestimates the value of ∆G° between the syn and anti conformers. The results are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated CH3OC(O)SCl with broad-band UV−visible irradiation produces an interconversion of the conformers, and the concomitant decomposition leads to formation of OCS and CO molecules.
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: Della Vedova, Carlos Omar. 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: Romano, Rosana Mariel. 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: Boese, Roland. Universitat Essen; Alemania
Fil: Oberhammer, Heinz. Eberhard Karls Universität Tübingen; Alemania
Fil: Willner, Helge. Universitat Essen; Alemania
Fil: Sala, Oswaldo. Universidade de Sao Paulo; Brasil
description The molecular structure and conformational properties of methoxycarbonylsulfenyl chloride, CH3OC(O)SCl, were determinated in the gas and solid phases by gas electron diffraction, low-temperature X-ray diffraction, and vibrational spectroscopy. Furthermore, quantum chemical calculations were performed. Experimental and theoretical methods result in structures with a planar C−O−C(O)−S−Cl skeleton. The electron diffraction intensities are reproduced best with a mixture of 72(8)% syn and 28(8)% anti conformers (S−Cl bond synperiplanar/antiperiplanar with respect to CdO bond) and the O−CH3 bond synperiplanar with respect to the CdO bond. The syn form is the preferred form and becomes the exclusive form in the crystalline solid at low temperature. This experimental result is reproduced very well by Hartree−Fock approximation and by density functional theory at different levels of theory but not by the MP2/6-311G* method, which overestimates the value of ∆G° between the syn and anti conformers. The results are discussed in terms of anomeric effects and a natural bond orbital (NBO) calculation. Photolysis of matrixisolated CH3OC(O)SCl with broad-band UV−visible irradiation produces an interconversion of the conformers, and the concomitant decomposition leads to formation of OCS and CO molecules.
publishDate 2002
dc.date.none.fl_str_mv 2002-12
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/11336/186615
Erben, Mauricio Federico; Della Vedova, Carlos Omar; Romano, Rosana Mariel; Boese, Roland; Oberhammer, Heinz; et al.; Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study; American Chemical Society; Inorganic Chemistry; 41; 5; 12-2002; 1064-1071
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/186615
identifier_str_mv Erben, Mauricio Federico; Della Vedova, Carlos Omar; Romano, Rosana Mariel; Boese, Roland; Oberhammer, Heinz; et al.; Anomeric and mesoneric effects in methoxycarbonylsulfenyl chloride, CH3OC(O)SCl. An experimental and theoretical study; American Chemical Society; Inorganic Chemistry; 41; 5; 12-2002; 1064-1071
0020-1669
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/ic010748y
info:eu-repo/semantics/altIdentifier/doi/10.1021/ic010748y
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
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
_version_ 1842981041993678848
score 12.48226

Publicaciones similares