Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS

Autores
Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Erben, Mauricio Federico; Lehmann, Christian W.; Bernhardt, Eduard; Beckers, Helmut; Willner, Helge; Della Vedova, Carlos Omar
Año de publicación
2010
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Fluorocarbonyl thio- and isothiocyanate, FC(O)SCN and FC(O)NCS, were fully characterized by IR (gas, Ar and N2 matrixes), Raman (liquid and solid), UV (gas), and 13C NMR (liquid) spectroscopy, as well as single-crystal X-ray diffraction. Their vibrational and conformational properties were analyzed using matrix isolation techniques guided by quantum chemical calculation at the ab initio [MP2 and CCSD(T)], density functional theory B3LYP, and CBS-QB3 levels of theory. A complete assignment of the fundamental modes of FC(O)SCN was performed. In both the gas and liquid states, FC(O)SCN and FC(O)NCS were found to exist as two conformers (Cs symmetry), in which the carbonyl double bond (C═O) adopts a synperiplanar (syn) and an antiperiplanar (anti) orientation with respect to either the SCN or NCS group. For FC(O)SCN, the conformational enthalpy difference, ΔH° = H°(anti) − H°(syn), was determined by matrix IR experiments to be 0.9 ± 0.2 kcal mol−1. The conformational equilibria were evaluated by fast-cooling gaseous samples highly diluted in argon at different temperatures as cryogenic matrixes. The conformational properties of both molecules were analyzed in terms of the hyperconjugative electronic effect applying the natural bond orbital method. The kinetics of the thermal conversion of the high-energy anti into the syn FC(O)NCS conformer was studied in Ar and N2 matrixes at cryogenic temperatures. The reversed syn → anti photoisomerization was observed using UV−vis light. Rearrangement of FC(O)SCN into FC(O)NCS was observed in the neat liquid and in solution. Under 193 nm (ArF excimer laser) irradiation, FC(O)NCS isolated in cryogenic Ar matrixes forms FC(O)SCN. At low temperature, single crystals of the two constitutional isomers were obtained using a miniature zone melting procedure. According to X-ray diffraction, they exclusively crystallize in their syn forms (Cs symmetry) in the orthorhombic crystal system.
Fil: Ramos, Luis A.. 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: Ulic, Sonia Elizabeth. 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. Universidad Nacional de Luján. Departamento de Ciencias Básicas; 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: 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: Lehmann, Christian W.. Max-Planck-Institut für Kohlenforschung; Alemania
Fil: Bernhardt, Eduard. Bergische Universität Wuppertal; Alemania
Fil: Beckers, Helmut. Bergische Universität Wuppertal; Alemania
Fil: Willner, Helge. Bergische Universität Wuppertal; Alemania
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
Materia
THEORETICAL CALCULATIONS
VIBRATIONAL PROPERTIES
CONFORMATIONAL AND CONSTITUTIONAL ISOMERISM
MATRIX ISOLATION
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:11336/278370
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/278370
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCSRamos, Luis A.Ulic, Sonia ElizabethRomano, Rosana MarielErben, Mauricio FedericoLehmann, Christian W.Bernhardt, EduardBeckers, HelmutWillner, HelgeDella Vedova, Carlos OmarTHEORETICAL CALCULATIONSVIBRATIONAL PROPERTIESCONFORMATIONAL AND CONSTITUTIONAL ISOMERISMMATRIX ISOLATIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Fluorocarbonyl thio- and isothiocyanate, FC(O)SCN and FC(O)NCS, were fully characterized by IR (gas, Ar and N2 matrixes), Raman (liquid and solid), UV (gas), and 13C NMR (liquid) spectroscopy, as well as single-crystal X-ray diffraction. Their vibrational and conformational properties were analyzed using matrix isolation techniques guided by quantum chemical calculation at the ab initio [MP2 and CCSD(T)], density functional theory B3LYP, and CBS-QB3 levels of theory. A complete assignment of the fundamental modes of FC(O)SCN was performed. In both the gas and liquid states, FC(O)SCN and FC(O)NCS were found to exist as two conformers (Cs symmetry), in which the carbonyl double bond (C═O) adopts a synperiplanar (syn) and an antiperiplanar (anti) orientation with respect to either the SCN or NCS group. For FC(O)SCN, the conformational enthalpy difference, ΔH° = H°(anti) − H°(syn), was determined by matrix IR experiments to be 0.9 ± 0.2 kcal mol−1. The conformational equilibria were evaluated by fast-cooling gaseous samples highly diluted in argon at different temperatures as cryogenic matrixes. The conformational properties of both molecules were analyzed in terms of the hyperconjugative electronic effect applying the natural bond orbital method. The kinetics of the thermal conversion of the high-energy anti into the syn FC(O)NCS conformer was studied in Ar and N2 matrixes at cryogenic temperatures. The reversed syn → anti photoisomerization was observed using UV−vis light. Rearrangement of FC(O)SCN into FC(O)NCS was observed in the neat liquid and in solution. Under 193 nm (ArF excimer laser) irradiation, FC(O)NCS isolated in cryogenic Ar matrixes forms FC(O)SCN. At low temperature, single crystals of the two constitutional isomers were obtained using a miniature zone melting procedure. According to X-ray diffraction, they exclusively crystallize in their syn forms (Cs symmetry) in the orthorhombic crystal system.Fil: Ramos, Luis A.. 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: Ulic, Sonia Elizabeth. 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. Universidad Nacional de Luján. Departamento de Ciencias Básicas; 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: 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: Lehmann, Christian W.. Max-Planck-Institut für Kohlenforschung; AlemaniaFil: Bernhardt, Eduard. Bergische Universität Wuppertal; AlemaniaFil: Beckers, Helmut. Bergische Universität Wuppertal; AlemaniaFil: Willner, Helge. Bergische Universität Wuppertal; AlemaniaFil: 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"; ArgentinaAmerican Chemical Society2010-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/278370Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Erben, Mauricio Federico; Lehmann, Christian W.; et al.; Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS; American Chemical Society; Inorganic Chemistry; 49; 23; 12-2010; 11142-111570020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic101741einfo:eu-repo/semantics/altIdentifier/doi/10.1021/ic101741einfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-02-06T12:03:36Zoai:ri.conicet.gov.ar:11336/278370instacron: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:34982026-02-06 12:03:37.135CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS
title Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS
spellingShingle Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS
Ramos, Luis A.
THEORETICAL CALCULATIONS
VIBRATIONAL PROPERTIES
CONFORMATIONAL AND CONSTITUTIONAL ISOMERISM
MATRIX ISOLATION
title_short Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS
title_full Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS
title_fullStr Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS
title_full_unstemmed Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS
title_sort Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS
dc.creator.none.fl_str_mv Ramos, Luis A.
Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Erben, Mauricio Federico
Lehmann, Christian W.
Bernhardt, Eduard
Beckers, Helmut
Willner, Helge
Della Vedova, Carlos Omar
author Ramos, Luis A.
author_facet Ramos, Luis A.
Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Erben, Mauricio Federico
Lehmann, Christian W.
Bernhardt, Eduard
Beckers, Helmut
Willner, Helge
Della Vedova, Carlos Omar
author_role author
author2 Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Erben, Mauricio Federico
Lehmann, Christian W.
Bernhardt, Eduard
Beckers, Helmut
Willner, Helge
Della Vedova, Carlos Omar
author2_role author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv THEORETICAL CALCULATIONS
VIBRATIONAL PROPERTIES
CONFORMATIONAL AND CONSTITUTIONAL ISOMERISM
MATRIX ISOLATION
topic THEORETICAL CALCULATIONS
VIBRATIONAL PROPERTIES
CONFORMATIONAL AND CONSTITUTIONAL ISOMERISM
MATRIX ISOLATION
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Fluorocarbonyl thio- and isothiocyanate, FC(O)SCN and FC(O)NCS, were fully characterized by IR (gas, Ar and N2 matrixes), Raman (liquid and solid), UV (gas), and 13C NMR (liquid) spectroscopy, as well as single-crystal X-ray diffraction. Their vibrational and conformational properties were analyzed using matrix isolation techniques guided by quantum chemical calculation at the ab initio [MP2 and CCSD(T)], density functional theory B3LYP, and CBS-QB3 levels of theory. A complete assignment of the fundamental modes of FC(O)SCN was performed. In both the gas and liquid states, FC(O)SCN and FC(O)NCS were found to exist as two conformers (Cs symmetry), in which the carbonyl double bond (C═O) adopts a synperiplanar (syn) and an antiperiplanar (anti) orientation with respect to either the SCN or NCS group. For FC(O)SCN, the conformational enthalpy difference, ΔH° = H°(anti) − H°(syn), was determined by matrix IR experiments to be 0.9 ± 0.2 kcal mol−1. The conformational equilibria were evaluated by fast-cooling gaseous samples highly diluted in argon at different temperatures as cryogenic matrixes. The conformational properties of both molecules were analyzed in terms of the hyperconjugative electronic effect applying the natural bond orbital method. The kinetics of the thermal conversion of the high-energy anti into the syn FC(O)NCS conformer was studied in Ar and N2 matrixes at cryogenic temperatures. The reversed syn → anti photoisomerization was observed using UV−vis light. Rearrangement of FC(O)SCN into FC(O)NCS was observed in the neat liquid and in solution. Under 193 nm (ArF excimer laser) irradiation, FC(O)NCS isolated in cryogenic Ar matrixes forms FC(O)SCN. At low temperature, single crystals of the two constitutional isomers were obtained using a miniature zone melting procedure. According to X-ray diffraction, they exclusively crystallize in their syn forms (Cs symmetry) in the orthorhombic crystal system.
Fil: Ramos, Luis A.. 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: Ulic, Sonia Elizabeth. 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. Universidad Nacional de Luján. Departamento de Ciencias Básicas; 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: 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: Lehmann, Christian W.. Max-Planck-Institut für Kohlenforschung; Alemania
Fil: Bernhardt, Eduard. Bergische Universität Wuppertal; Alemania
Fil: Beckers, Helmut. Bergische Universität Wuppertal; Alemania
Fil: Willner, Helge. Bergische Universität Wuppertal; Alemania
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
description Fluorocarbonyl thio- and isothiocyanate, FC(O)SCN and FC(O)NCS, were fully characterized by IR (gas, Ar and N2 matrixes), Raman (liquid and solid), UV (gas), and 13C NMR (liquid) spectroscopy, as well as single-crystal X-ray diffraction. Their vibrational and conformational properties were analyzed using matrix isolation techniques guided by quantum chemical calculation at the ab initio [MP2 and CCSD(T)], density functional theory B3LYP, and CBS-QB3 levels of theory. A complete assignment of the fundamental modes of FC(O)SCN was performed. In both the gas and liquid states, FC(O)SCN and FC(O)NCS were found to exist as two conformers (Cs symmetry), in which the carbonyl double bond (C═O) adopts a synperiplanar (syn) and an antiperiplanar (anti) orientation with respect to either the SCN or NCS group. For FC(O)SCN, the conformational enthalpy difference, ΔH° = H°(anti) − H°(syn), was determined by matrix IR experiments to be 0.9 ± 0.2 kcal mol−1. The conformational equilibria were evaluated by fast-cooling gaseous samples highly diluted in argon at different temperatures as cryogenic matrixes. The conformational properties of both molecules were analyzed in terms of the hyperconjugative electronic effect applying the natural bond orbital method. The kinetics of the thermal conversion of the high-energy anti into the syn FC(O)NCS conformer was studied in Ar and N2 matrixes at cryogenic temperatures. The reversed syn → anti photoisomerization was observed using UV−vis light. Rearrangement of FC(O)SCN into FC(O)NCS was observed in the neat liquid and in solution. Under 193 nm (ArF excimer laser) irradiation, FC(O)NCS isolated in cryogenic Ar matrixes forms FC(O)SCN. At low temperature, single crystals of the two constitutional isomers were obtained using a miniature zone melting procedure. According to X-ray diffraction, they exclusively crystallize in their syn forms (Cs symmetry) in the orthorhombic crystal system.
publishDate 2010
dc.date.none.fl_str_mv 2010-12
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/11336/278370
Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Erben, Mauricio Federico; Lehmann, Christian W.; et al.; Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS; American Chemical Society; Inorganic Chemistry; 49; 23; 12-2010; 11142-11157
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/278370
identifier_str_mv Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Erben, Mauricio Federico; Lehmann, Christian W.; et al.; Vibrational Spectra, Crystal Structures, Constitutional and Rotational Isomerism of FC(O)SCN and FC(O)NCS; American Chemical Society; Inorganic Chemistry; 49; 23; 12-2010; 11142-11157
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/ic101741e
info:eu-repo/semantics/altIdentifier/doi/10.1021/ic101741e
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
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 13.106097

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