Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies

Autores
Ramos Guerrero, Luis Alejandro; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Vishnevskiy, Yuri V.; Berger, Raphael J.; Mitzel, Norbert W.; Beckers, Helmut; Willner, Helge; Tong, Shengrui; Ge, Maofa; Della Védova, Carlos Omar
Año de publicación
2012
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO, was prepared by the reaction of ClF2CC(O)Cl with excess of AgNCO. The colorless compound melts at -83 °C and the vapor pressure follows the equation ln p = -3868.3 (1/T) + 10.89 (p [Atm], T [K]) in the range -38 to +22 °C, extrapolated bp ca. 82 °C. It has been characterized by IR (gas phase, Ar matrix), liquid Raman, 19F and 13C NMR, gas UV-vis spectrum, photoelectron spectroscopy (PES), photoionization mass spectrometry (PIMS), and gas electron diffraction (GED). The matrix photochemistry has been studied and the conformational properties of ClF2CC(O)NCO have been analyzed by joint application of vibrational spectroscopy, GED, and quantum chemical calculations. Two conformers were detected in gaseous and liquid phases, in which the C-Cl bond adopts a gauche orientation with respect to the C=O group, whereas this group can be in syn or anti orientation with respect to the N=C bond of the NCO group. An enthalpy difference δHexp° = 1.3 ± 0.2 kcal mol-1 between the most stable syn-gauche and the less stable anti-gauche form was derived using the van't Hoff equation, which is in reasonable agreement with the computed difference of δH° = 0.8 kcal mol-1 (B3LYP/6-311+G(3df) approximation). The most significant gas phase structural parameters for gauche-syn ClF2CC(O)NCO are re(NC=O) = 1.157(1) Å, re(N=CO) = 1.218(1) Å, re(N-C) = 1.378(9) Å, re(C=O) = 1.195(1) Å,e(CNC) = 128.6(19)°. Photolysis of ClF 2CC(O)NCO using an ArF excimer laser (193 nm) mainly yield ClF 2CNCO along with some ClF2CC(O)N nitrene. The valence electronic properties of the title compound were studied using the PES and PIMS. The experimental first vertical ionization energy of 11.54 eV corresponds to the ejection of a carbonylic oxygen lone pair electron.
Fil: Ramos Guerrero, Luis Alejandro. 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
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: Vishnevskiy, Yuri V.. Universitat Bielefeld; Alemania
Fil: Berger, Raphael J.. Universitat Bielefeld; Alemania
Fil: Mitzel, Norbert W.. Universitat Bielefeld; Alemania
Fil: Beckers, Helmut. Universität Wuppertal; Alemania
Fil: Willner, Helge. Universität Wuppertal; Alemania
Fil: Tong, Shengrui. Chinese Academy of Sciences; República de China
Fil: Ge, Maofa. 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
Chlorodifluoroacetyl Isocyanate
Matrix Photochemistr
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:11336/82380
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/82380
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studiesRamos Guerrero, Luis AlejandroUlic, Sonia ElizabethRomano, Rosana MarielVishnevskiy, Yuri V.Berger, Raphael J.Mitzel, Norbert W.Beckers, HelmutWillner, HelgeTong, ShengruiGe, MaofaDella Védova, Carlos OmarChlorodifluoroacetyl IsocyanateMatrix PhotochemistrSpectroscopyhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO, was prepared by the reaction of ClF2CC(O)Cl with excess of AgNCO. The colorless compound melts at -83 °C and the vapor pressure follows the equation ln p = -3868.3 (1/T) + 10.89 (p [Atm], T [K]) in the range -38 to +22 °C, extrapolated bp ca. 82 °C. It has been characterized by IR (gas phase, Ar matrix), liquid Raman, 19F and 13C NMR, gas UV-vis spectrum, photoelectron spectroscopy (PES), photoionization mass spectrometry (PIMS), and gas electron diffraction (GED). The matrix photochemistry has been studied and the conformational properties of ClF2CC(O)NCO have been analyzed by joint application of vibrational spectroscopy, GED, and quantum chemical calculations. Two conformers were detected in gaseous and liquid phases, in which the C-Cl bond adopts a gauche orientation with respect to the C=O group, whereas this group can be in syn or anti orientation with respect to the N=C bond of the NCO group. An enthalpy difference δHexp° = 1.3 ± 0.2 kcal mol-1 between the most stable syn-gauche and the less stable anti-gauche form was derived using the van't Hoff equation, which is in reasonable agreement with the computed difference of δH° = 0.8 kcal mol-1 (B3LYP/6-311+G(3df) approximation). The most significant gas phase structural parameters for gauche-syn ClF2CC(O)NCO are re(NC=O) = 1.157(1) Å, re(N=CO) = 1.218(1) Å, re(N-C) = 1.378(9) Å, re(C=O) = 1.195(1) Å,e(CNC) = 128.6(19)°. Photolysis of ClF 2CC(O)NCO using an ArF excimer laser (193 nm) mainly yield ClF 2CNCO along with some ClF2CC(O)N nitrene. The valence electronic properties of the title compound were studied using the PES and PIMS. The experimental first vertical ionization energy of 11.54 eV corresponds to the ejection of a carbonylic oxygen lone pair electron.Fil: Ramos Guerrero, Luis Alejandro. 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"; 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: Vishnevskiy, Yuri V.. Universitat Bielefeld; AlemaniaFil: Berger, Raphael J.. Universitat Bielefeld; AlemaniaFil: Mitzel, Norbert W.. Universitat Bielefeld; AlemaniaFil: Beckers, Helmut. Universität Wuppertal; AlemaniaFil: Willner, Helge. Universität Wuppertal; AlemaniaFil: Tong, Shengrui. Chinese Academy of Sciences; República de ChinaFil: Ge, Maofa. 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 Society2012-11-01info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/82380Ramos Guerrero, Luis Alejandro; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Vishnevskiy, Yuri V.; Berger, Raphael J.; et al.; Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies; American Chemical Society; Journal of Physical Chemistry A; 116; 47; 1-11-2012; 11586-115951089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jp3096055info:eu-repo/semantics/altIdentifier/doi/10.1021/jp3096055info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:54:28Zoai:ri.conicet.gov.ar:11336/82380instacron: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:34982025-09-03 09:54:29.33CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies
title Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies
spellingShingle Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies
Ramos Guerrero, Luis Alejandro
Chlorodifluoroacetyl Isocyanate
Matrix Photochemistr
Spectroscopy
title_short Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies
title_full Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies
title_fullStr Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies
title_full_unstemmed Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies
title_sort Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies
dc.creator.none.fl_str_mv Ramos Guerrero, Luis Alejandro
Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Vishnevskiy, Yuri V.
Berger, Raphael J.
Mitzel, Norbert W.
Beckers, Helmut
Willner, Helge
Tong, Shengrui
Ge, Maofa
Della Védova, Carlos Omar
author Ramos Guerrero, Luis Alejandro
author_facet Ramos Guerrero, Luis Alejandro
Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Vishnevskiy, Yuri V.
Berger, Raphael J.
Mitzel, Norbert W.
Beckers, Helmut
Willner, Helge
Tong, Shengrui
Ge, Maofa
Della Védova, Carlos Omar
author_role author
author2 Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Vishnevskiy, Yuri V.
Berger, Raphael J.
Mitzel, Norbert W.
Beckers, Helmut
Willner, Helge
Tong, Shengrui
Ge, Maofa
Della Védova, Carlos Omar
author2_role author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Chlorodifluoroacetyl Isocyanate
Matrix Photochemistr
Spectroscopy
topic Chlorodifluoroacetyl Isocyanate
Matrix Photochemistr
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 Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO, was prepared by the reaction of ClF2CC(O)Cl with excess of AgNCO. The colorless compound melts at -83 °C and the vapor pressure follows the equation ln p = -3868.3 (1/T) + 10.89 (p [Atm], T [K]) in the range -38 to +22 °C, extrapolated bp ca. 82 °C. It has been characterized by IR (gas phase, Ar matrix), liquid Raman, 19F and 13C NMR, gas UV-vis spectrum, photoelectron spectroscopy (PES), photoionization mass spectrometry (PIMS), and gas electron diffraction (GED). The matrix photochemistry has been studied and the conformational properties of ClF2CC(O)NCO have been analyzed by joint application of vibrational spectroscopy, GED, and quantum chemical calculations. Two conformers were detected in gaseous and liquid phases, in which the C-Cl bond adopts a gauche orientation with respect to the C=O group, whereas this group can be in syn or anti orientation with respect to the N=C bond of the NCO group. An enthalpy difference δHexp° = 1.3 ± 0.2 kcal mol-1 between the most stable syn-gauche and the less stable anti-gauche form was derived using the van't Hoff equation, which is in reasonable agreement with the computed difference of δH° = 0.8 kcal mol-1 (B3LYP/6-311+G(3df) approximation). The most significant gas phase structural parameters for gauche-syn ClF2CC(O)NCO are re(NC=O) = 1.157(1) Å, re(N=CO) = 1.218(1) Å, re(N-C) = 1.378(9) Å, re(C=O) = 1.195(1) Å,e(CNC) = 128.6(19)°. Photolysis of ClF 2CC(O)NCO using an ArF excimer laser (193 nm) mainly yield ClF 2CNCO along with some ClF2CC(O)N nitrene. The valence electronic properties of the title compound were studied using the PES and PIMS. The experimental first vertical ionization energy of 11.54 eV corresponds to the ejection of a carbonylic oxygen lone pair electron.
Fil: Ramos Guerrero, Luis Alejandro. 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
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: Vishnevskiy, Yuri V.. Universitat Bielefeld; Alemania
Fil: Berger, Raphael J.. Universitat Bielefeld; Alemania
Fil: Mitzel, Norbert W.. Universitat Bielefeld; Alemania
Fil: Beckers, Helmut. Universität Wuppertal; Alemania
Fil: Willner, Helge. Universität Wuppertal; Alemania
Fil: Tong, Shengrui. Chinese Academy of Sciences; República de China
Fil: Ge, Maofa. 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 Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO, was prepared by the reaction of ClF2CC(O)Cl with excess of AgNCO. The colorless compound melts at -83 °C and the vapor pressure follows the equation ln p = -3868.3 (1/T) + 10.89 (p [Atm], T [K]) in the range -38 to +22 °C, extrapolated bp ca. 82 °C. It has been characterized by IR (gas phase, Ar matrix), liquid Raman, 19F and 13C NMR, gas UV-vis spectrum, photoelectron spectroscopy (PES), photoionization mass spectrometry (PIMS), and gas electron diffraction (GED). The matrix photochemistry has been studied and the conformational properties of ClF2CC(O)NCO have been analyzed by joint application of vibrational spectroscopy, GED, and quantum chemical calculations. Two conformers were detected in gaseous and liquid phases, in which the C-Cl bond adopts a gauche orientation with respect to the C=O group, whereas this group can be in syn or anti orientation with respect to the N=C bond of the NCO group. An enthalpy difference δHexp° = 1.3 ± 0.2 kcal mol-1 between the most stable syn-gauche and the less stable anti-gauche form was derived using the van't Hoff equation, which is in reasonable agreement with the computed difference of δH° = 0.8 kcal mol-1 (B3LYP/6-311+G(3df) approximation). The most significant gas phase structural parameters for gauche-syn ClF2CC(O)NCO are re(NC=O) = 1.157(1) Å, re(N=CO) = 1.218(1) Å, re(N-C) = 1.378(9) Å, re(C=O) = 1.195(1) Å,e(CNC) = 128.6(19)°. Photolysis of ClF 2CC(O)NCO using an ArF excimer laser (193 nm) mainly yield ClF 2CNCO along with some ClF2CC(O)N nitrene. The valence electronic properties of the title compound were studied using the PES and PIMS. The experimental first vertical ionization energy of 11.54 eV corresponds to the ejection of a carbonylic oxygen lone pair electron.
publishDate 2012
dc.date.none.fl_str_mv 2012-11-01
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/11336/82380
Ramos Guerrero, Luis Alejandro; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Vishnevskiy, Yuri V.; Berger, Raphael J.; et al.; Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies; American Chemical Society; Journal of Physical Chemistry A; 116; 47; 1-11-2012; 11586-11595
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/82380
identifier_str_mv Ramos Guerrero, Luis Alejandro; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Vishnevskiy, Yuri V.; Berger, Raphael J.; et al.; Chlorodifluoroacetyl isocyanate, ClF2CC(O)NCO: Preparation and structural and spectroscopic studies; American Chemical Society; Journal of Physical Chemistry A; 116; 47; 1-11-2012; 11586-11595
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/jp3096055
info:eu-repo/semantics/altIdentifier/doi/10.1021/jp3096055
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 13.13397

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