Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies

Autores
Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana M.; Vishnevskiy, Yury V.; Mitzel, Norbert W.; Beckers, Helmut; Willner, Helge; Tong, Shengrui; Ge, Maofa; Della Védova, Carlos Omar
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Chlorodifluoroacetyl isothiocyanate, ClF2CC(O)NCS, was synthesized by the reaction of ClF2CC(O)Cl with an excess of AgNCS. The colorless product melts at −85 °C, and its vapor pressure follows the equation ln p = −4471.1 (1/T) + 11.35 (p [atm], T [K]) in the range −38 to 22 °C. The compound has been characterized by IR (gas phase, Ar matrix, and matrix photochemistry), by liquid Raman, by 19F and 13C NMR, gas UV−vis, and photoelectron spectroscopy (PES), by photoionization mass spectrometry (PIMS), and by gas electron diffraction (GED). The conformational properties of ClF2CC(O)NCS have been analyzed by joint application of vibrational spectroscopy, GED and quantum chemical calculations. The existence of two conformers has been detected in the gas and liquid phases, in which the C−Cl bond adopts a gauche orientation with respect to the CO group; the CO group is in syn- or anti-position with respect to the NC double bond of the NCS group. The computed ΔG° difference between these two gauche−syn and gauche−anti forms is ΔG° = 0.63 kcal mol−1 in the B3LYP/6-31G(d) approximation. The most significant gas-phase structural parameters for gauche−syn ClF2CC(O)NCS are re(NCS) 1.559(2) Å, re(NCS) 1.213(2) Å, re(NC) 1.399(7) Å, re(CO) 1.199(2) Å, and ∠e(CNC) 134.7(13)°. Photolysis of ClF2CC(O)NCS using an ArF excimer laser (193 nm) mainly yields ClF2CNCS, CO, and ClC(O)CF2NCS. The valence electronic properties of the title compound were studied using PES and PIMS. The experimental first vertical ionization energy of 10.43 eV corresponds to the ejection primarily of the sulfur lone-pair electrons of the in-plane nonbonding orbital on the NCS group.
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
Fil: Romano, Rosana M.. 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, Yury V.. Universitat Bielefeld; Alemania
Fil: Mitzel, Norbert W.. Universitat Bielefeld; Alemania
Fil: Beckers, Helmut. Bergische Universitat Wuppertal; Alemania
Fil: Willner, Helge. Bergische Universitat 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 Isothiocyanate
Spectroscopic
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:11336/24495
Acceder
id CONICETDig_8a6833fc93cbd73550de3124f371f02e
oai_identifier_str oai:ri.conicet.gov.ar:11336/24495
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic StudiesRamos, Luis A.Ulic, Sonia ElizabethRomano, Rosana M.Vishnevskiy, Yury V.Mitzel, Norbert W.Beckers, HelmutWillner, HelgeTong, ShengruiGe, MaofaDella Védova, Carlos OmarChlorodifluoroacetyl IsothiocyanateSpectroscopichttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Chlorodifluoroacetyl isothiocyanate, ClF2CC(O)NCS, was synthesized by the reaction of ClF2CC(O)Cl with an excess of AgNCS. The colorless product melts at −85 °C, and its vapor pressure follows the equation ln p = −4471.1 (1/T) + 11.35 (p [atm], T [K]) in the range −38 to 22 °C. The compound has been characterized by IR (gas phase, Ar matrix, and matrix photochemistry), by liquid Raman, by 19F and 13C NMR, gas UV−vis, and photoelectron spectroscopy (PES), by photoionization mass spectrometry (PIMS), and by gas electron diffraction (GED). The conformational properties of ClF2CC(O)NCS have been analyzed by joint application of vibrational spectroscopy, GED and quantum chemical calculations. The existence of two conformers has been detected in the gas and liquid phases, in which the C−Cl bond adopts a gauche orientation with respect to the CO group; the CO group is in syn- or anti-position with respect to the NC double bond of the NCS group. The computed ΔG° difference between these two gauche−syn and gauche−anti forms is ΔG° = 0.63 kcal mol−1 in the B3LYP/6-31G(d) approximation. The most significant gas-phase structural parameters for gauche−syn ClF2CC(O)NCS are re(NCS) 1.559(2) Å, re(NCS) 1.213(2) Å, re(NC) 1.399(7) Å, re(CO) 1.199(2) Å, and ∠e(CNC) 134.7(13)°. Photolysis of ClF2CC(O)NCS using an ArF excimer laser (193 nm) mainly yields ClF2CNCS, CO, and ClC(O)CF2NCS. The valence electronic properties of the title compound were studied using PES and PIMS. The experimental first vertical ionization energy of 10.43 eV corresponds to the ejection primarily of the sulfur lone-pair electrons of the in-plane nonbonding orbital on the NCS group.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"; ArgentinaFil: Romano, Rosana M.. 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, Yury V.. Universitat Bielefeld; AlemaniaFil: Mitzel, Norbert W.. Universitat Bielefeld; AlemaniaFil: Beckers, Helmut. Bergische Universitat Wuppertal; AlemaniaFil: Willner, Helge. Bergische Universitat 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 Society2013-06info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/24495Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana M.; Vishnevskiy, Yury V.; Mitzel, Norbert W.; et al.; Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies; American Chemical Society; Journal of Physical Chemistry A; 117; 27; 6-2013; 5597-56061089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1021/jp403549finfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp403549finfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-10T13:10:47Zoai:ri.conicet.gov.ar:11336/24495instacron: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:34982025-09-10 13:10:47.514CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
title Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
spellingShingle Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
Ramos, Luis A.
Chlorodifluoroacetyl Isothiocyanate
Spectroscopic
title_short Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
title_full Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
title_fullStr Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
title_full_unstemmed Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
title_sort Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies
dc.creator.none.fl_str_mv Ramos, Luis A.
Ulic, Sonia Elizabeth
Romano, Rosana M.
Vishnevskiy, Yury V.
Mitzel, Norbert W.
Beckers, Helmut
Willner, Helge
Tong, Shengrui
Ge, Maofa
Della Védova, Carlos Omar
author Ramos, Luis A.
author_facet Ramos, Luis A.
Ulic, Sonia Elizabeth
Romano, Rosana M.
Vishnevskiy, Yury V.
Mitzel, Norbert W.
Beckers, Helmut
Willner, Helge
Tong, Shengrui
Ge, Maofa
Della Védova, Carlos Omar
author_role author
author2 Ulic, Sonia Elizabeth
Romano, Rosana M.
Vishnevskiy, Yury V.
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
dc.subject.none.fl_str_mv Chlorodifluoroacetyl Isothiocyanate
Spectroscopic
topic Chlorodifluoroacetyl Isothiocyanate
Spectroscopic
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 isothiocyanate, ClF2CC(O)NCS, was synthesized by the reaction of ClF2CC(O)Cl with an excess of AgNCS. The colorless product melts at −85 °C, and its vapor pressure follows the equation ln p = −4471.1 (1/T) + 11.35 (p [atm], T [K]) in the range −38 to 22 °C. The compound has been characterized by IR (gas phase, Ar matrix, and matrix photochemistry), by liquid Raman, by 19F and 13C NMR, gas UV−vis, and photoelectron spectroscopy (PES), by photoionization mass spectrometry (PIMS), and by gas electron diffraction (GED). The conformational properties of ClF2CC(O)NCS have been analyzed by joint application of vibrational spectroscopy, GED and quantum chemical calculations. The existence of two conformers has been detected in the gas and liquid phases, in which the C−Cl bond adopts a gauche orientation with respect to the CO group; the CO group is in syn- or anti-position with respect to the NC double bond of the NCS group. The computed ΔG° difference between these two gauche−syn and gauche−anti forms is ΔG° = 0.63 kcal mol−1 in the B3LYP/6-31G(d) approximation. The most significant gas-phase structural parameters for gauche−syn ClF2CC(O)NCS are re(NCS) 1.559(2) Å, re(NCS) 1.213(2) Å, re(NC) 1.399(7) Å, re(CO) 1.199(2) Å, and ∠e(CNC) 134.7(13)°. Photolysis of ClF2CC(O)NCS using an ArF excimer laser (193 nm) mainly yields ClF2CNCS, CO, and ClC(O)CF2NCS. The valence electronic properties of the title compound were studied using PES and PIMS. The experimental first vertical ionization energy of 10.43 eV corresponds to the ejection primarily of the sulfur lone-pair electrons of the in-plane nonbonding orbital on the NCS group.
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
Fil: Romano, Rosana M.. 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, Yury V.. Universitat Bielefeld; Alemania
Fil: Mitzel, Norbert W.. Universitat Bielefeld; Alemania
Fil: Beckers, Helmut. Bergische Universitat Wuppertal; Alemania
Fil: Willner, Helge. Bergische Universitat 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 isothiocyanate, ClF2CC(O)NCS, was synthesized by the reaction of ClF2CC(O)Cl with an excess of AgNCS. The colorless product melts at −85 °C, and its vapor pressure follows the equation ln p = −4471.1 (1/T) + 11.35 (p [atm], T [K]) in the range −38 to 22 °C. The compound has been characterized by IR (gas phase, Ar matrix, and matrix photochemistry), by liquid Raman, by 19F and 13C NMR, gas UV−vis, and photoelectron spectroscopy (PES), by photoionization mass spectrometry (PIMS), and by gas electron diffraction (GED). The conformational properties of ClF2CC(O)NCS have been analyzed by joint application of vibrational spectroscopy, GED and quantum chemical calculations. The existence of two conformers has been detected in the gas and liquid phases, in which the C−Cl bond adopts a gauche orientation with respect to the CO group; the CO group is in syn- or anti-position with respect to the NC double bond of the NCS group. The computed ΔG° difference between these two gauche−syn and gauche−anti forms is ΔG° = 0.63 kcal mol−1 in the B3LYP/6-31G(d) approximation. The most significant gas-phase structural parameters for gauche−syn ClF2CC(O)NCS are re(NCS) 1.559(2) Å, re(NCS) 1.213(2) Å, re(NC) 1.399(7) Å, re(CO) 1.199(2) Å, and ∠e(CNC) 134.7(13)°. Photolysis of ClF2CC(O)NCS using an ArF excimer laser (193 nm) mainly yields ClF2CNCS, CO, and ClC(O)CF2NCS. The valence electronic properties of the title compound were studied using PES and PIMS. The experimental first vertical ionization energy of 10.43 eV corresponds to the ejection primarily of the sulfur lone-pair electrons of the in-plane nonbonding orbital on the NCS group.
publishDate 2013
dc.date.none.fl_str_mv 2013-06
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/11336/24495
Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana M.; Vishnevskiy, Yury V.; Mitzel, Norbert W.; et al.; Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies; American Chemical Society; Journal of Physical Chemistry A; 117; 27; 6-2013; 5597-5606
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/24495
identifier_str_mv Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana M.; Vishnevskiy, Yury V.; Mitzel, Norbert W.; et al.; Chlorodifluoroacetyl Isothiocyanate, ClF2CC(O)NCS: Preparation and Structural and Spectroscopic Studies; American Chemical Society; Journal of Physical Chemistry A; 117; 27; 6-2013; 5597-5606
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/doi/10.1021/jp403549f
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp403549f
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 12.993085

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