Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation

Autores
Spaltro, Agustín; Pelúas, Melina Gisella; Della Vedova, Carlos Omar; Romano, Rosana Mariel
Año de publicación
2024
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The conformations of trifluoroacetyl triflate, CF3C(O)OSO2CF3, were investigated through experimental vibrational methods (gas-phase FTIR, liquid-phase Raman, and Ar matrix FTIR spectroscopy) and density functional theory (DFT) calculations. A potential energy surface was computed using the B3P86/6-31+g(d) approximation as a function of the dihedral angles τ1 = CC−OS and τ2 = CO−SC. The surface reveals three minima, which were further optimized using the B3LYP method with various basis sets (6-31++G(d), 6-311++G(d), tzvp, and cc-pvtz). The global minimum corresponds to a syn–anti conformer (the C=O double-bound syn with respect the O−S single bond and the C−O single bond anti with respect to S−C single bond). The other two minima represent enantiomeric syn–gauche forms. The Ar matrix FTIR spectrum exhibited clear evidence of the presence of two conformers. Furthermore, the randomization process observed following broadband UV–visible irradiation facilitated the identification of the IR absorption of each conformer. Based on the Ar matrix FTIR experiments, the vapour phase of trifluoroacetyl triflate at room temperature was composed of approximately 60–70% of the syn–anti conformer and 30–40% of the syn–gauche form.
Fil: Spaltro, Agustín. 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: Pelúas, Melina Gisella. 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
Materia
conformations
matrix FTIR
gas-phase FTIR
Raman
DFT
Nivel de accesibilidad
acceso abierto
Condiciones de uso
https://creativecommons.org/licenses/by/2.5/ar/
Repositorio
CONICET Digital (CONICET)
Institución
Consejo Nacional de Investigaciones Científicas y Técnicas
OAI Identificador
oai:ri.conicet.gov.ar:11336/238992
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/238992
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT InvestigationSpaltro, AgustínPelúas, Melina GisellaDella Vedova, Carlos OmarRomano, Rosana Marielconformationsmatrix FTIRgas-phase FTIRRamanDFThttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The conformations of trifluoroacetyl triflate, CF3C(O)OSO2CF3, were investigated through experimental vibrational methods (gas-phase FTIR, liquid-phase Raman, and Ar matrix FTIR spectroscopy) and density functional theory (DFT) calculations. A potential energy surface was computed using the B3P86/6-31+g(d) approximation as a function of the dihedral angles τ1 = CC−OS and τ2 = CO−SC. The surface reveals three minima, which were further optimized using the B3LYP method with various basis sets (6-31++G(d), 6-311++G(d), tzvp, and cc-pvtz). The global minimum corresponds to a syn–anti conformer (the C=O double-bound syn with respect the O−S single bond and the C−O single bond anti with respect to S−C single bond). The other two minima represent enantiomeric syn–gauche forms. The Ar matrix FTIR spectrum exhibited clear evidence of the presence of two conformers. Furthermore, the randomization process observed following broadband UV–visible irradiation facilitated the identification of the IR absorption of each conformer. Based on the Ar matrix FTIR experiments, the vapour phase of trifluoroacetyl triflate at room temperature was composed of approximately 60–70% of the syn–anti conformer and 30–40% of the syn–gauche form.Fil: Spaltro, Agustín. 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: Pelúas, Melina Gisella. 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"; ArgentinaMDPI2024-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/238992Spaltro, Agustín; Pelúas, Melina Gisella; Della Vedova, Carlos Omar; Romano, Rosana Mariel; Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation; MDPI; Spectroscopy Journal; 2; 2; 6-2024; 68-812813-446XCONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://www.mdpi.com/2813-446X/2/2/5info:eu-repo/semantics/altIdentifier/doi/10.3390/spectroscj2020005info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:45:56Zoai:ri.conicet.gov.ar:11336/238992instacron: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:34982025-10-15 14:45:57.202CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
title Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
spellingShingle Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
Spaltro, Agustín
conformations
matrix FTIR
gas-phase FTIR
Raman
DFT
title_short Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
title_full Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
title_fullStr Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
title_full_unstemmed Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
title_sort Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation
dc.creator.none.fl_str_mv Spaltro, Agustín
Pelúas, Melina Gisella
Della Vedova, Carlos Omar
Romano, Rosana Mariel
author Spaltro, Agustín
author_facet Spaltro, Agustín
Pelúas, Melina Gisella
Della Vedova, Carlos Omar
Romano, Rosana Mariel
author_role author
author2 Pelúas, Melina Gisella
Della Vedova, Carlos Omar
Romano, Rosana Mariel
author2_role author
author
author
dc.subject.none.fl_str_mv conformations
matrix FTIR
gas-phase FTIR
Raman
DFT
topic conformations
matrix FTIR
gas-phase FTIR
Raman
DFT
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 conformations of trifluoroacetyl triflate, CF3C(O)OSO2CF3, were investigated through experimental vibrational methods (gas-phase FTIR, liquid-phase Raman, and Ar matrix FTIR spectroscopy) and density functional theory (DFT) calculations. A potential energy surface was computed using the B3P86/6-31+g(d) approximation as a function of the dihedral angles τ1 = CC−OS and τ2 = CO−SC. The surface reveals three minima, which were further optimized using the B3LYP method with various basis sets (6-31++G(d), 6-311++G(d), tzvp, and cc-pvtz). The global minimum corresponds to a syn–anti conformer (the C=O double-bound syn with respect the O−S single bond and the C−O single bond anti with respect to S−C single bond). The other two minima represent enantiomeric syn–gauche forms. The Ar matrix FTIR spectrum exhibited clear evidence of the presence of two conformers. Furthermore, the randomization process observed following broadband UV–visible irradiation facilitated the identification of the IR absorption of each conformer. Based on the Ar matrix FTIR experiments, the vapour phase of trifluoroacetyl triflate at room temperature was composed of approximately 60–70% of the syn–anti conformer and 30–40% of the syn–gauche form.
Fil: Spaltro, Agustín. 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: Pelúas, Melina Gisella. 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
description The conformations of trifluoroacetyl triflate, CF3C(O)OSO2CF3, were investigated through experimental vibrational methods (gas-phase FTIR, liquid-phase Raman, and Ar matrix FTIR spectroscopy) and density functional theory (DFT) calculations. A potential energy surface was computed using the B3P86/6-31+g(d) approximation as a function of the dihedral angles τ1 = CC−OS and τ2 = CO−SC. The surface reveals three minima, which were further optimized using the B3LYP method with various basis sets (6-31++G(d), 6-311++G(d), tzvp, and cc-pvtz). The global minimum corresponds to a syn–anti conformer (the C=O double-bound syn with respect the O−S single bond and the C−O single bond anti with respect to S−C single bond). The other two minima represent enantiomeric syn–gauche forms. The Ar matrix FTIR spectrum exhibited clear evidence of the presence of two conformers. Furthermore, the randomization process observed following broadband UV–visible irradiation facilitated the identification of the IR absorption of each conformer. Based on the Ar matrix FTIR experiments, the vapour phase of trifluoroacetyl triflate at room temperature was composed of approximately 60–70% of the syn–anti conformer and 30–40% of the syn–gauche form.
publishDate 2024
dc.date.none.fl_str_mv 2024-06
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/11336/238992
Spaltro, Agustín; Pelúas, Melina Gisella; Della Vedova, Carlos Omar; Romano, Rosana Mariel; Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation; MDPI; Spectroscopy Journal; 2; 2; 6-2024; 68-81
2813-446X
CONICET Digital
CONICET
url http://hdl.handle.net/11336/238992
identifier_str_mv Spaltro, Agustín; Pelúas, Melina Gisella; Della Vedova, Carlos Omar; Romano, Rosana Mariel; Conformational Analysis of Trifluoroacetyl Triflate, CF3C(O)OSO2CF3: Experimental Vibrational and DFT Investigation; MDPI; Spectroscopy Journal; 2; 2; 6-2024; 68-81
2813-446X
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://www.mdpi.com/2813-446X/2/2/5
info:eu-repo/semantics/altIdentifier/doi/10.3390/spectroscj2020005
dc.rights.none.fl_str_mv info:eu-repo/semantics/openAccess
https://creativecommons.org/licenses/by/2.5/ar/
eu_rights_str_mv openAccess
rights_invalid_str_mv https://creativecommons.org/licenses/by/2.5/ar/
dc.format.none.fl_str_mv application/pdf
application/pdf
dc.publisher.none.fl_str_mv MDPI
publisher.none.fl_str_mv MDPI
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 13.22299

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