Molecular and Electronic Structure of ä-Valerothiolactone

Autores
Dugarte Jiménez, Nahir Yerely; Erben, Mauricio Federico; Boese, Roland; Ge, Mao-Fa; Yao, Li; Della Védova, Carlos Omar
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The crystal structure of the six-member heterocyclic δ-valerothiolactone (1-thiocycloalkan-2-one) compound has been determined by X-ray diffraction at low temperature, revealing that its skeleton adopts a half-chair conformation. The conformation around the thioester group is almost planar with an anti orientation of the C═O double bond with respect the S−C single bond [C(2)−S(1)−C(6)−O(1) = 176.26(8)°]. The skeletal parameters, especially valence angles [∠C5−C6−S = 121.19(6)°, ∠O═C6−C5 = 122.25(8)°, ∠C6−S−C2 = 106.80(4)°], differ from those typically found in acyclic thioester compounds, symptomatic of the presence of strain effects. The conventional ring strain energy was determined to be 7.5 kcal/mol at the MP2/6-311++G(d,p) level of calculation within the hyperhomodesmotic model approximation. Moreover, the valence electronic structure was investigated by HeI photoelectron spectroscopy assisted by quantum chemical calculations at the OVGF/6-311++G(d,p) level of theory. The first three bands at 9.35, 9.50, and 11.53 eV denote ionizations related with the nS, nO, and πC═O orbitals, respectively, demonstrating the importance of the −SC(O)− group in the outermost electronic properties.
Fil: Dugarte Jiménez, Nahir Yerely. 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: Boese, Roland. Universität Duisburg-Essen; Alemania
Fil: Ge, Mao-Fa. Chinese Academy of Sciences; República de China
Fil: Yao, Li. Chinese Academy of Sciences; República de China
Fil: Della Védova, 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
Materia
CRYSTAL STRUCTURE
MOLECULES
CONFORMATION
ENERGY
MOLECULAR STRUCTURE
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:11336/104109
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/104109
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Molecular and Electronic Structure of ä-ValerothiolactoneDugarte Jiménez, Nahir YerelyErben, Mauricio FedericoBoese, RolandGe, Mao-FaYao, LiDella Védova, Carlos OmarCRYSTAL STRUCTUREMOLECULESCONFORMATIONENERGYMOLECULAR STRUCTUREhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The crystal structure of the six-member heterocyclic δ-valerothiolactone (1-thiocycloalkan-2-one) compound has been determined by X-ray diffraction at low temperature, revealing that its skeleton adopts a half-chair conformation. The conformation around the thioester group is almost planar with an anti orientation of the C═O double bond with respect the S−C single bond [C(2)−S(1)−C(6)−O(1) = 176.26(8)°]. The skeletal parameters, especially valence angles [∠C5−C6−S = 121.19(6)°, ∠O═C6−C5 = 122.25(8)°, ∠C6−S−C2 = 106.80(4)°], differ from those typically found in acyclic thioester compounds, symptomatic of the presence of strain effects. The conventional ring strain energy was determined to be 7.5 kcal/mol at the MP2/6-311++G(d,p) level of calculation within the hyperhomodesmotic model approximation. Moreover, the valence electronic structure was investigated by HeI photoelectron spectroscopy assisted by quantum chemical calculations at the OVGF/6-311++G(d,p) level of theory. The first three bands at 9.35, 9.50, and 11.53 eV denote ionizations related with the nS, nO, and πC═O orbitals, respectively, demonstrating the importance of the −SC(O)− group in the outermost electronic properties.Fil: Dugarte Jiménez, Nahir Yerely. 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: Boese, Roland. Universität Duisburg-Essen; AlemaniaFil: Ge, Mao-Fa. Chinese Academy of Sciences; República de ChinaFil: Yao, Li. Chinese Academy of Sciences; República de ChinaFil: Della Védova, 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"; ArgentinaAmerican Chemical Society2010-11-04info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/104109Dugarte Jiménez, Nahir Yerely; Erben, Mauricio Federico; Boese, Roland; Ge, Mao-Fa; Yao, Li; et al.; Molecular and Electronic Structure of ä-Valerothiolactone; American Chemical Society; Journal of Physical Chemistry A; 114; 4-11-2010; 12540-125471089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp108885sinfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp108885sinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-29T09:55:42Zoai:ri.conicet.gov.ar:11336/104109instacron: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:34982025-09-29 09:55:43.032CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Molecular and Electronic Structure of ä-Valerothiolactone
title Molecular and Electronic Structure of ä-Valerothiolactone
spellingShingle Molecular and Electronic Structure of ä-Valerothiolactone
Dugarte Jiménez, Nahir Yerely
CRYSTAL STRUCTURE
MOLECULES
CONFORMATION
ENERGY
MOLECULAR STRUCTURE
title_short Molecular and Electronic Structure of ä-Valerothiolactone
title_full Molecular and Electronic Structure of ä-Valerothiolactone
title_fullStr Molecular and Electronic Structure of ä-Valerothiolactone
title_full_unstemmed Molecular and Electronic Structure of ä-Valerothiolactone
title_sort Molecular and Electronic Structure of ä-Valerothiolactone
dc.creator.none.fl_str_mv Dugarte Jiménez, Nahir Yerely
Erben, Mauricio Federico
Boese, Roland
Ge, Mao-Fa
Yao, Li
Della Védova, Carlos Omar
author Dugarte Jiménez, Nahir Yerely
author_facet Dugarte Jiménez, Nahir Yerely
Erben, Mauricio Federico
Boese, Roland
Ge, Mao-Fa
Yao, Li
Della Védova, Carlos Omar
author_role author
author2 Erben, Mauricio Federico
Boese, Roland
Ge, Mao-Fa
Yao, Li
Della Védova, Carlos Omar
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv CRYSTAL STRUCTURE
MOLECULES
CONFORMATION
ENERGY
MOLECULAR STRUCTURE
topic CRYSTAL STRUCTURE
MOLECULES
CONFORMATION
ENERGY
MOLECULAR STRUCTURE
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 crystal structure of the six-member heterocyclic δ-valerothiolactone (1-thiocycloalkan-2-one) compound has been determined by X-ray diffraction at low temperature, revealing that its skeleton adopts a half-chair conformation. The conformation around the thioester group is almost planar with an anti orientation of the C═O double bond with respect the S−C single bond [C(2)−S(1)−C(6)−O(1) = 176.26(8)°]. The skeletal parameters, especially valence angles [∠C5−C6−S = 121.19(6)°, ∠O═C6−C5 = 122.25(8)°, ∠C6−S−C2 = 106.80(4)°], differ from those typically found in acyclic thioester compounds, symptomatic of the presence of strain effects. The conventional ring strain energy was determined to be 7.5 kcal/mol at the MP2/6-311++G(d,p) level of calculation within the hyperhomodesmotic model approximation. Moreover, the valence electronic structure was investigated by HeI photoelectron spectroscopy assisted by quantum chemical calculations at the OVGF/6-311++G(d,p) level of theory. The first three bands at 9.35, 9.50, and 11.53 eV denote ionizations related with the nS, nO, and πC═O orbitals, respectively, demonstrating the importance of the −SC(O)− group in the outermost electronic properties.
Fil: Dugarte Jiménez, Nahir Yerely. 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: Boese, Roland. Universität Duisburg-Essen; Alemania
Fil: Ge, Mao-Fa. Chinese Academy of Sciences; República de China
Fil: Yao, Li. Chinese Academy of Sciences; República de China
Fil: Della Védova, 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
description The crystal structure of the six-member heterocyclic δ-valerothiolactone (1-thiocycloalkan-2-one) compound has been determined by X-ray diffraction at low temperature, revealing that its skeleton adopts a half-chair conformation. The conformation around the thioester group is almost planar with an anti orientation of the C═O double bond with respect the S−C single bond [C(2)−S(1)−C(6)−O(1) = 176.26(8)°]. The skeletal parameters, especially valence angles [∠C5−C6−S = 121.19(6)°, ∠O═C6−C5 = 122.25(8)°, ∠C6−S−C2 = 106.80(4)°], differ from those typically found in acyclic thioester compounds, symptomatic of the presence of strain effects. The conventional ring strain energy was determined to be 7.5 kcal/mol at the MP2/6-311++G(d,p) level of calculation within the hyperhomodesmotic model approximation. Moreover, the valence electronic structure was investigated by HeI photoelectron spectroscopy assisted by quantum chemical calculations at the OVGF/6-311++G(d,p) level of theory. The first three bands at 9.35, 9.50, and 11.53 eV denote ionizations related with the nS, nO, and πC═O orbitals, respectively, demonstrating the importance of the −SC(O)− group in the outermost electronic properties.
publishDate 2010
dc.date.none.fl_str_mv 2010-11-04
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/11336/104109
Dugarte Jiménez, Nahir Yerely; Erben, Mauricio Federico; Boese, Roland; Ge, Mao-Fa; Yao, Li; et al.; Molecular and Electronic Structure of ä-Valerothiolactone; American Chemical Society; Journal of Physical Chemistry A; 114; 4-11-2010; 12540-12547
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/104109
identifier_str_mv Dugarte Jiménez, Nahir Yerely; Erben, Mauricio Federico; Boese, Roland; Ge, Mao-Fa; Yao, Li; et al.; Molecular and Electronic Structure of ä-Valerothiolactone; American Chemical Society; Journal of Physical Chemistry A; 114; 4-11-2010; 12540-12547
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/jp108885s
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp108885s
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
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 13.070432

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