Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS

Autores
Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Erben, Mauricio Federico; Vishnevskiy, Yuri V.; Reuter, Christian G.; Mitzel, Norbert W.; Beckers, Helmut; Willner, Helge; Zeng, Xiaoqing; Bernhardt, Eduard; Ge, Maofa; Tong, Shengrui; Della Védova, Carlos Omar
Año de publicación
2013
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Chlorocarbonylthio- and isothiocyanate (ClC(O)SCN and ClC(O)- NCS) have been isolated and characterized by IR (Ar matrix, gas), Raman (liquid), 13C NMR and UV−visible spectroscopies. Vibrational and quantum chemical studies suggest the presence of the syn and anti conformers (SCN group with respect to the CO bond) in the gas phase for both constitutional isomers. syn-ClC(O)SCN is preferred by ΔH° (anti/syn) = 1.3(0.3) kcal mol−1 . The solid-state structure of ClC(O)SCN has been determined by single crystal X-ray diffraction analysis at low temperature. The crystalline solid consists exclusively of molecules in the syn conformation. On the other hand, the anti form is more stable for the ClC(O)NCS isomer. The structure of ClC(O)NCS and its conformational composition were determined by gas electron diffraction. An unusual low syn → anti interconversion energy barrier of 0.98 (0.15) kcal mol−1 was detected for ClC(O)NCS at cryogenic temperatures. The photochemistry of both constitutional isomers isolated in solid argon at 15 K was studied. Rearrangement of ClC(O)SCN to ClC(O)NCS was observed in the neat liquid and under UV−vis irradiation of ClC(O)SCN isolated in solid argon. Properties have been discussed in terms of the valence electronic structure, including the analysis of the He(I) photoelectron spectrum of ClC(O)SCN
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; 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: Vishnevskiy, Yuri V.. Universitat Bielefeld; Alemania
Fil: Reuter, Christian G.. 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: Zeng, Xiaoqing. Bergische Universitat Wuppertal; Alemania
Fil: Bernhardt, Eduard. Bergische Universitat Wuppertal; Alemania
Fil: Ge, Maofa. Chinese Academy of Sciences. Institute of Chemistry; China
Fil: Tong, Shengrui. Chinese Academy of Sciences. Institute of Chemistry; 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
Chemistry
Spectroscopy
Physical Chemistry
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:11336/23927
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/23927
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network_name_str CONICET Digital (CONICET)
spelling Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCSRamos, Luis A.Ulic, Sonia ElizabethRomano, Rosana MarielErben, Mauricio FedericoVishnevskiy, Yuri V.Reuter, Christian G.Mitzel, Norbert W.Beckers, HelmutWillner, HelgeZeng, XiaoqingBernhardt, EduardGe, MaofaTong, ShengruiDella Védova, Carlos OmarChemistrySpectroscopyPhysical Chemistryhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Chlorocarbonylthio- and isothiocyanate (ClC(O)SCN and ClC(O)- NCS) have been isolated and characterized by IR (Ar matrix, gas), Raman (liquid), 13C NMR and UV−visible spectroscopies. Vibrational and quantum chemical studies suggest the presence of the syn and anti conformers (SCN group with respect to the CO bond) in the gas phase for both constitutional isomers. syn-ClC(O)SCN is preferred by ΔH° (anti/syn) = 1.3(0.3) kcal mol−1 . The solid-state structure of ClC(O)SCN has been determined by single crystal X-ray diffraction analysis at low temperature. The crystalline solid consists exclusively of molecules in the syn conformation. On the other hand, the anti form is more stable for the ClC(O)NCS isomer. The structure of ClC(O)NCS and its conformational composition were determined by gas electron diffraction. An unusual low syn → anti interconversion energy barrier of 0.98 (0.15) kcal mol−1 was detected for ClC(O)NCS at cryogenic temperatures. The photochemistry of both constitutional isomers isolated in solid argon at 15 K was studied. Rearrangement of ClC(O)SCN to ClC(O)NCS was observed in the neat liquid and under UV−vis irradiation of ClC(O)SCN isolated in solid argon. Properties have been discussed in terms of the valence electronic structure, including the analysis of the He(I) photoelectron spectrum of ClC(O)SCNFil: 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; 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: Vishnevskiy, Yuri V.. Universitat Bielefeld; AlemaniaFil: Reuter, Christian G.. Universitat Bielefeld; AlemaniaFil: Mitzel, Norbert W.. Universitat Bielefeld; AlemaniaFil: Beckers, Helmut. Bergische Universitat Wuppertal; AlemaniaFil: Willner, Helge. Bergische Universitat Wuppertal; AlemaniaFil: Zeng, Xiaoqing. Bergische Universitat Wuppertal; AlemaniaFil: Bernhardt, Eduard. Bergische Universitat Wuppertal; AlemaniaFil: Ge, Maofa. Chinese Academy of Sciences. Institute of Chemistry; ChinaFil: Tong, Shengrui. Chinese Academy of Sciences. Institute of Chemistry; 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 Society2013-02-17info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/23927Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Erben, Mauricio Federico; Vishnevskiy, Yuri V.; et al.; Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS; American Chemical Society; Journal of Physical Chemistry A; 117; 11; 17-2-2013; 2383-23991089-5639CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi//10.1021/jp400281ginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp400281ginfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:23:28Zoai:ri.conicet.gov.ar:11336/23927instacron: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:34982025-10-22 11:23:28.415CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
title Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
spellingShingle Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
Ramos, Luis A.
Chemistry
Spectroscopy
Physical Chemistry
title_short Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
title_full Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
title_fullStr Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
title_full_unstemmed Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
title_sort Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS
dc.creator.none.fl_str_mv Ramos, Luis A.
Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Erben, Mauricio Federico
Vishnevskiy, Yuri V.
Reuter, Christian G.
Mitzel, Norbert W.
Beckers, Helmut
Willner, Helge
Zeng, Xiaoqing
Bernhardt, Eduard
Ge, Maofa
Tong, Shengrui
Della Védova, Carlos Omar
author Ramos, Luis A.
author_facet Ramos, Luis A.
Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Erben, Mauricio Federico
Vishnevskiy, Yuri V.
Reuter, Christian G.
Mitzel, Norbert W.
Beckers, Helmut
Willner, Helge
Zeng, Xiaoqing
Bernhardt, Eduard
Ge, Maofa
Tong, Shengrui
Della Védova, Carlos Omar
author_role author
author2 Ulic, Sonia Elizabeth
Romano, Rosana Mariel
Erben, Mauricio Federico
Vishnevskiy, Yuri V.
Reuter, Christian G.
Mitzel, Norbert W.
Beckers, Helmut
Willner, Helge
Zeng, Xiaoqing
Bernhardt, Eduard
Ge, Maofa
Tong, Shengrui
Della Védova, Carlos Omar
author2_role author
author
author
author
author
author
author
author
author
author
author
author
author
dc.subject.none.fl_str_mv Chemistry
Spectroscopy
Physical Chemistry
topic Chemistry
Spectroscopy
Physical Chemistry
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Chlorocarbonylthio- and isothiocyanate (ClC(O)SCN and ClC(O)- NCS) have been isolated and characterized by IR (Ar matrix, gas), Raman (liquid), 13C NMR and UV−visible spectroscopies. Vibrational and quantum chemical studies suggest the presence of the syn and anti conformers (SCN group with respect to the CO bond) in the gas phase for both constitutional isomers. syn-ClC(O)SCN is preferred by ΔH° (anti/syn) = 1.3(0.3) kcal mol−1 . The solid-state structure of ClC(O)SCN has been determined by single crystal X-ray diffraction analysis at low temperature. The crystalline solid consists exclusively of molecules in the syn conformation. On the other hand, the anti form is more stable for the ClC(O)NCS isomer. The structure of ClC(O)NCS and its conformational composition were determined by gas electron diffraction. An unusual low syn → anti interconversion energy barrier of 0.98 (0.15) kcal mol−1 was detected for ClC(O)NCS at cryogenic temperatures. The photochemistry of both constitutional isomers isolated in solid argon at 15 K was studied. Rearrangement of ClC(O)SCN to ClC(O)NCS was observed in the neat liquid and under UV−vis irradiation of ClC(O)SCN isolated in solid argon. Properties have been discussed in terms of the valence electronic structure, including the analysis of the He(I) photoelectron spectrum of ClC(O)SCN
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; 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: Vishnevskiy, Yuri V.. Universitat Bielefeld; Alemania
Fil: Reuter, Christian G.. 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: Zeng, Xiaoqing. Bergische Universitat Wuppertal; Alemania
Fil: Bernhardt, Eduard. Bergische Universitat Wuppertal; Alemania
Fil: Ge, Maofa. Chinese Academy of Sciences. Institute of Chemistry; China
Fil: Tong, Shengrui. Chinese Academy of Sciences. Institute of Chemistry; 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 Chlorocarbonylthio- and isothiocyanate (ClC(O)SCN and ClC(O)- NCS) have been isolated and characterized by IR (Ar matrix, gas), Raman (liquid), 13C NMR and UV−visible spectroscopies. Vibrational and quantum chemical studies suggest the presence of the syn and anti conformers (SCN group with respect to the CO bond) in the gas phase for both constitutional isomers. syn-ClC(O)SCN is preferred by ΔH° (anti/syn) = 1.3(0.3) kcal mol−1 . The solid-state structure of ClC(O)SCN has been determined by single crystal X-ray diffraction analysis at low temperature. The crystalline solid consists exclusively of molecules in the syn conformation. On the other hand, the anti form is more stable for the ClC(O)NCS isomer. The structure of ClC(O)NCS and its conformational composition were determined by gas electron diffraction. An unusual low syn → anti interconversion energy barrier of 0.98 (0.15) kcal mol−1 was detected for ClC(O)NCS at cryogenic temperatures. The photochemistry of both constitutional isomers isolated in solid argon at 15 K was studied. Rearrangement of ClC(O)SCN to ClC(O)NCS was observed in the neat liquid and under UV−vis irradiation of ClC(O)SCN isolated in solid argon. Properties have been discussed in terms of the valence electronic structure, including the analysis of the He(I) photoelectron spectrum of ClC(O)SCN
publishDate 2013
dc.date.none.fl_str_mv 2013-02-17
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/11336/23927
Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Erben, Mauricio Federico; Vishnevskiy, Yuri V.; et al.; Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS; American Chemical Society; Journal of Physical Chemistry A; 117; 11; 17-2-2013; 2383-2399
1089-5639
CONICET Digital
CONICET
url http://hdl.handle.net/11336/23927
identifier_str_mv Ramos, Luis A.; Ulic, Sonia Elizabeth; Romano, Rosana Mariel; Erben, Mauricio Federico; Vishnevskiy, Yuri V.; et al.; Spectroscopic Characterization and Constitutional and Rotational Isomerism of ClC(O)SCN and ClC(O)NCS; American Chemical Society; Journal of Physical Chemistry A; 117; 11; 17-2-2013; 2383-2399
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/jp400281g
info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/jp400281g
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 12.982451

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