Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases

Autores
Arce, Valeria Beatriz; Della Vedova, Carlos Omar; Downs, Anthony J.; Parsons, Simon; Romano, Rosana Mariel
Año de publicación
2006
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The conformational properties of gaseous trichloromethyl chloroformate (or “diphosgene”), ClC(O)- OCCl3, have been studied by vibrational spectroscopy [IR (gas), IR (matrix), and Raman (liquid)] and quantum chemical calculations (MP2 and B3LYP with 6-311G* basis sets); in addition, the structure of a single crystal at low temperature has been determined by X-ray diffraction. ClC(O)OCCl3 exhibits only one conformational form having Cs symmetry with a synperiplanar orientation of the C-O single bond relative to the CdO double bond. The calculated energy difference between the syn and anti forms, 5.73 kcal mol-1 (B3LYP) or 7.06 kcal mol-1 (MP2), is consistent with the experimental findings for the gas and liquid phases. The crystalline solid at 150 K [monoclinic, P21/n, a ) 5.5578(5) Å, b ) 14.2895(12) Å, c ) 8.6246(7) Å, â ) 102.443(2)°, Z ) 4] likewise consists only of molecules in the syn form.
Fil: Arce, Valeria Beatriz. 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. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Servicios a la Industria y al Sistema Científico; Argentina
Fil: Downs, Anthony J.. University of Oxford; Reino Unido
Fil: Parsons, Simon. University of Edinburgh; Reino Unido
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
DIPHOSGENE
VIBRATIONAL SPECTROSCOPY
QUANTUM CHEMICAL CALCULATIONS
SYN FORM
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:11336/186636
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/186636
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phasesArce, Valeria BeatrizDella Vedova, Carlos OmarDowns, Anthony J.Parsons, SimonRomano, Rosana MarielDIPHOSGENEVIBRATIONAL SPECTROSCOPYQUANTUM CHEMICAL CALCULATIONSSYN FORMhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The conformational properties of gaseous trichloromethyl chloroformate (or “diphosgene”), ClC(O)- OCCl3, have been studied by vibrational spectroscopy [IR (gas), IR (matrix), and Raman (liquid)] and quantum chemical calculations (MP2 and B3LYP with 6-311G* basis sets); in addition, the structure of a single crystal at low temperature has been determined by X-ray diffraction. ClC(O)OCCl3 exhibits only one conformational form having Cs symmetry with a synperiplanar orientation of the C-O single bond relative to the CdO double bond. The calculated energy difference between the syn and anti forms, 5.73 kcal mol-1 (B3LYP) or 7.06 kcal mol-1 (MP2), is consistent with the experimental findings for the gas and liquid phases. The crystalline solid at 150 K [monoclinic, P21/n, a ) 5.5578(5) Å, b ) 14.2895(12) Å, c ) 8.6246(7) Å, â ) 102.443(2)°, Z ) 4] likewise consists only of molecules in the syn form.Fil: Arce, Valeria Beatriz. 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"; Argentina. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Servicios a la Industria y al Sistema Científico; ArgentinaFil: Downs, Anthony J.. University of Oxford; Reino UnidoFil: Parsons, Simon. University of Edinburgh; Reino UnidoFil: 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"; ArgentinaAmerican Chemical Society2006-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/186636Arce, Valeria Beatriz; Della Vedova, Carlos Omar; Downs, Anthony J.; Parsons, Simon; Romano, Rosana Mariel; Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases; American Chemical Society; Journal of Organic Chemistry; 71; 9; 12-2006; 3423-34280022-3263CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/jo052260ainfo:eu-repo/semantics/altIdentifier/doi/10.1021/jo052260ainfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-22T11:53:40Zoai:ri.conicet.gov.ar:11336/186636instacron: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 11:53:41.175CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases
title Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases
spellingShingle Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases
Arce, Valeria Beatriz
DIPHOSGENE
VIBRATIONAL SPECTROSCOPY
QUANTUM CHEMICAL CALCULATIONS
SYN FORM
title_short Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases
title_full Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases
title_fullStr Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases
title_full_unstemmed Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases
title_sort Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases
dc.creator.none.fl_str_mv Arce, Valeria Beatriz
Della Vedova, Carlos Omar
Downs, Anthony J.
Parsons, Simon
Romano, Rosana Mariel
author Arce, Valeria Beatriz
author_facet Arce, Valeria Beatriz
Della Vedova, Carlos Omar
Downs, Anthony J.
Parsons, Simon
Romano, Rosana Mariel
author_role author
author2 Della Vedova, Carlos Omar
Downs, Anthony J.
Parsons, Simon
Romano, Rosana Mariel
author2_role author
author
author
author
dc.subject.none.fl_str_mv DIPHOSGENE
VIBRATIONAL SPECTROSCOPY
QUANTUM CHEMICAL CALCULATIONS
SYN FORM
topic DIPHOSGENE
VIBRATIONAL SPECTROSCOPY
QUANTUM CHEMICAL CALCULATIONS
SYN FORM
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 conformational properties of gaseous trichloromethyl chloroformate (or “diphosgene”), ClC(O)- OCCl3, have been studied by vibrational spectroscopy [IR (gas), IR (matrix), and Raman (liquid)] and quantum chemical calculations (MP2 and B3LYP with 6-311G* basis sets); in addition, the structure of a single crystal at low temperature has been determined by X-ray diffraction. ClC(O)OCCl3 exhibits only one conformational form having Cs symmetry with a synperiplanar orientation of the C-O single bond relative to the CdO double bond. The calculated energy difference between the syn and anti forms, 5.73 kcal mol-1 (B3LYP) or 7.06 kcal mol-1 (MP2), is consistent with the experimental findings for the gas and liquid phases. The crystalline solid at 150 K [monoclinic, P21/n, a ) 5.5578(5) Å, b ) 14.2895(12) Å, c ) 8.6246(7) Å, â ) 102.443(2)°, Z ) 4] likewise consists only of molecules in the syn form.
Fil: Arce, Valeria Beatriz. 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. Universidad Nacional de La Plata. Facultad de Ciencias Exactas. Departamento de Química. Laboratorio de Servicios a la Industria y al Sistema Científico; Argentina
Fil: Downs, Anthony J.. University of Oxford; Reino Unido
Fil: Parsons, Simon. University of Edinburgh; Reino Unido
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 conformational properties of gaseous trichloromethyl chloroformate (or “diphosgene”), ClC(O)- OCCl3, have been studied by vibrational spectroscopy [IR (gas), IR (matrix), and Raman (liquid)] and quantum chemical calculations (MP2 and B3LYP with 6-311G* basis sets); in addition, the structure of a single crystal at low temperature has been determined by X-ray diffraction. ClC(O)OCCl3 exhibits only one conformational form having Cs symmetry with a synperiplanar orientation of the C-O single bond relative to the CdO double bond. The calculated energy difference between the syn and anti forms, 5.73 kcal mol-1 (B3LYP) or 7.06 kcal mol-1 (MP2), is consistent with the experimental findings for the gas and liquid phases. The crystalline solid at 150 K [monoclinic, P21/n, a ) 5.5578(5) Å, b ) 14.2895(12) Å, c ) 8.6246(7) Å, â ) 102.443(2)°, Z ) 4] likewise consists only of molecules in the syn form.
publishDate 2006
dc.date.none.fl_str_mv 2006-12
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/11336/186636
Arce, Valeria Beatriz; Della Vedova, Carlos Omar; Downs, Anthony J.; Parsons, Simon; Romano, Rosana Mariel; Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases; American Chemical Society; Journal of Organic Chemistry; 71; 9; 12-2006; 3423-3428
0022-3263
CONICET Digital
CONICET
url http://hdl.handle.net/11336/186636
identifier_str_mv Arce, Valeria Beatriz; Della Vedova, Carlos Omar; Downs, Anthony J.; Parsons, Simon; Romano, Rosana Mariel; Trichloromethyl chloroformate ("diphosgene"), ClC(O)OCCl 3: Structure and conformational properties in the gaseous and condensed phases; American Chemical Society; Journal of Organic Chemistry; 71; 9; 12-2006; 3423-3428
0022-3263
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/jo052260a
info:eu-repo/semantics/altIdentifier/doi/10.1021/jo052260a
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
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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