Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferab...

Autores
Galván, J E.; Contreras Aguilar, Elizabeth; Defonsi Lestard, M. E.; Tuttolomondo, M. E.; Ulic, Sonia Elizabeth; Ben Altabef, A.
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Methyl trifluoromethanethiosulfonate, CF3SO2SCH3, was synthesized and characterized by 13C NMR, 19F NMR, and vibrational spectroscopy. This structural study was supported by MP2 and DFT (B3LYP and MPW1PW91) calculations, which revealed a strong dependence of the theoretical structure on the polarization of the basis set. Theoretical data indicate that only one conformer, gauche, is predicted by rotating around the S–S bond. This conformational preference was studied using the total energy scheme and natural bond orbital partition scheme. These results evidence that electron delocalization and especially LP S → σ∗ C(1)-S interactions play an interesting role in the reactivity-structure connection of oxoesters and thioesters. Gas and liquid infrared and liquid Raman spectra were recorded and assigned. The experimental vibrational data along with theoretical force constants (B3LYP) were used to define a scaled quantum mechanical force field, which enabled the reproduction of the measured frequencies with a final root-mean-square deviation of 8.06 cm−1.
Centro de Química Inorgánica
Materia
Química
NBO calculations
IR spectroscopy
Raman spectroscopy
Ab initio calculations
Nivel de accesibilidad
acceso abierto
Condiciones de uso
http://creativecommons.org/licenses/by-nc-sa/4.0/
Repositorio
SEDICI (UNLP)
Institución
Universidad Nacional de La Plata
OAI Identificador
oai:sedici.unlp.edu.ar:10915/103037
Acceder
id SEDICI_4d3dc90157e0b1d944f3656f0e8c096d
oai_identifier_str oai:sedici.unlp.edu.ar:10915/103037
network_acronym_str SEDICI
repository_id_str 1329
network_name_str SEDICI (UNLP)
spelling Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compoundsGalván, J E.Contreras Aguilar, ElizabethDefonsi Lestard, M. E.Tuttolomondo, M. E.Ulic, Sonia ElizabethBen Altabef, A.QuímicaNBO calculationsIR spectroscopyRaman spectroscopyAb initio calculationsMethyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>, was synthesized and characterized by <sup>13</sup>C NMR, <sup>19</sup>F NMR, and vibrational spectroscopy. This structural study was supported by MP2 and DFT (B3LYP and MPW1PW91) calculations, which revealed a strong dependence of the theoretical structure on the polarization of the basis set. Theoretical data indicate that only one conformer, gauche, is predicted by rotating around the S–S bond. This conformational preference was studied using the total energy scheme and natural bond orbital partition scheme. These results evidence that electron delocalization and especially LP S → σ∗ C(1)-S interactions play an interesting role in the reactivity-structure connection of oxoesters and thioesters. Gas and liquid infrared and liquid Raman spectra were recorded and assigned. The experimental vibrational data along with theoretical force constants (B3LYP) were used to define a scaled quantum mechanical force field, which enabled the reproduction of the measured frequencies with a final root-mean-square deviation of 8.06 cm<sup>−1</sup>.Centro de Química Inorgánica2017-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionArticulohttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdf254-261http://sedici.unlp.edu.ar/handle/10915/103037enginfo:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0020169316306855?via%3Dihubinfo:eu-repo/semantics/altIdentifier/issn/0020-1693info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ica.2016.10.020info:eu-repo/semantics/openAccesshttp://creativecommons.org/licenses/by-nc-sa/4.0/Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)reponame:SEDICI (UNLP)instname:Universidad Nacional de La Platainstacron:UNLP2025-09-03T10:54:33Zoai:sedici.unlp.edu.ar:10915/103037Institucionalhttp://sedici.unlp.edu.ar/Universidad públicaNo correspondehttp://sedici.unlp.edu.ar/oai/snrdalira@sedici.unlp.edu.arArgentinaNo correspondeNo correspondeNo correspondeopendoar:13292025-09-03 10:54:34.003SEDICI (UNLP) - Universidad Nacional de La Platafalse
dc.title.none.fl_str_mv Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compounds
title Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compounds
spellingShingle Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compounds
Galván, J E.
Química
NBO calculations
IR spectroscopy
Raman spectroscopy
Ab initio calculations
title_short Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compounds
title_full Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compounds
title_fullStr Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compounds
title_full_unstemmed Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compounds
title_sort Theoretical and experimental study of a new thiosulfonate derivative: Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>. : Conformational transferability in CX<sub>3</sub>SO<sub>2</sub>S-R compounds
dc.creator.none.fl_str_mv Galván, J E.
Contreras Aguilar, Elizabeth
Defonsi Lestard, M. E.
Tuttolomondo, M. E.
Ulic, Sonia Elizabeth
Ben Altabef, A.
author Galván, J E.
author_facet Galván, J E.
Contreras Aguilar, Elizabeth
Defonsi Lestard, M. E.
Tuttolomondo, M. E.
Ulic, Sonia Elizabeth
Ben Altabef, A.
author_role author
author2 Contreras Aguilar, Elizabeth
Defonsi Lestard, M. E.
Tuttolomondo, M. E.
Ulic, Sonia Elizabeth
Ben Altabef, A.
author2_role author
author
author
author
author
dc.subject.none.fl_str_mv Química
NBO calculations
IR spectroscopy
Raman spectroscopy
Ab initio calculations
topic Química
NBO calculations
IR spectroscopy
Raman spectroscopy
Ab initio calculations
dc.description.none.fl_txt_mv Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>, was synthesized and characterized by <sup>13</sup>C NMR, <sup>19</sup>F NMR, and vibrational spectroscopy. This structural study was supported by MP2 and DFT (B3LYP and MPW1PW91) calculations, which revealed a strong dependence of the theoretical structure on the polarization of the basis set. Theoretical data indicate that only one conformer, gauche, is predicted by rotating around the S–S bond. This conformational preference was studied using the total energy scheme and natural bond orbital partition scheme. These results evidence that electron delocalization and especially LP S → σ∗ C(1)-S interactions play an interesting role in the reactivity-structure connection of oxoesters and thioesters. Gas and liquid infrared and liquid Raman spectra were recorded and assigned. The experimental vibrational data along with theoretical force constants (B3LYP) were used to define a scaled quantum mechanical force field, which enabled the reproduction of the measured frequencies with a final root-mean-square deviation of 8.06 cm<sup>−1</sup>.
Centro de Química Inorgánica
description Methyl trifluoromethanethiosulfonate, CF<sub>3</sub>SO<sub>2</sub>SCH<sub>3</sub>, was synthesized and characterized by <sup>13</sup>C NMR, <sup>19</sup>F NMR, and vibrational spectroscopy. This structural study was supported by MP2 and DFT (B3LYP and MPW1PW91) calculations, which revealed a strong dependence of the theoretical structure on the polarization of the basis set. Theoretical data indicate that only one conformer, gauche, is predicted by rotating around the S–S bond. This conformational preference was studied using the total energy scheme and natural bond orbital partition scheme. These results evidence that electron delocalization and especially LP S → σ∗ C(1)-S interactions play an interesting role in the reactivity-structure connection of oxoesters and thioesters. Gas and liquid infrared and liquid Raman spectra were recorded and assigned. The experimental vibrational data along with theoretical force constants (B3LYP) were used to define a scaled quantum mechanical force field, which enabled the reproduction of the measured frequencies with a final root-mean-square deviation of 8.06 cm<sup>−1</sup>.
publishDate 2017
dc.date.none.fl_str_mv 2017-01
dc.type.none.fl_str_mv info:eu-repo/semantics/article
info:eu-repo/semantics/publishedVersion
Articulo
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://sedici.unlp.edu.ar/handle/10915/103037
url http://sedici.unlp.edu.ar/handle/10915/103037
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/abs/pii/S0020169316306855?via%3Dihub
info:eu-repo/semantics/altIdentifier/issn/0020-1693
info:eu-repo/semantics/altIdentifier/doi/10.1016/j.ica.2016.10.020
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
eu_rights_str_mv openAccess
rights_invalid_str_mv http://creativecommons.org/licenses/by-nc-sa/4.0/
Creative Commons Attribution-NonCommercial-ShareAlike 4.0 International (CC BY-NC-SA 4.0)
dc.format.none.fl_str_mv application/pdf
254-261
dc.source.none.fl_str_mv reponame:SEDICI (UNLP)
instname:Universidad Nacional de La Plata
instacron:UNLP
reponame_str SEDICI (UNLP)
collection SEDICI (UNLP)
instname_str Universidad Nacional de La Plata
instacron_str UNLP
institution UNLP
repository.name.fl_str_mv SEDICI (UNLP) - Universidad Nacional de La Plata
repository.mail.fl_str_mv alira@sedici.unlp.edu.ar
_version_ 1842260431618441216
score 13.13397

Publicaciones similares