Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2

Autores
Robles, Norma Lis; Cutin, Edgardo Hugo; Alvarez, Rosa Maria Susana; Oberhammer, Heinz
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
Vibrational spectra [FT IR (gas and liquid); FT Raman (liquid)] and quantum chemical calculations at different levels of theory (HF, B3LYP and MP2 using 6-31G(d), 6-311 + G(2df) and cc-pVTZ base sets) demonstrate that N-(chloroformyl) iminosulfur dichloride (ClC(O)NSCl2) is present in the fluid phases as a mixture of syn–syn and syn–anti forms (syn orientation of the CN bond with respect to the ClSCl bisector; syn or anti orientation of the carbonyl group with respect to the NS bond). From the relative IR intensities of the CO stretching bands the contribution of the syn-anti form is calculated to be 6(2)% in the gas, corresponding to a Gibbs free energy difference ΔG° = G°syn–anti − G°syn–syn = 1.6(3) kcal/mol. This value is reproduced very well by quantum chemical calculations which include electron correlation effects (ΔG° = 1.59–1.91 kcal/mol). The HF approximation overestimates this energy difference (ΔG° = 4.45 kcal/mol). On the basis of theoretical calculations and reported data for other iminosulfur dichlorides, a complete assignment of the fundamental modes for ClC(O)NSCl2 is proposed.
Fil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Alvarez, Rosa Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Oberhammer, Heinz. Universität Tübingen; Alemania
Materia
Computational Chemistry
Conformational Properties
N-(Chloroformyl) Iminosulfur Dichloride
Vibrational Spectra
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:11336/54509
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/54509
network_acronym_str CONICETDig
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network_name_str CONICET Digital (CONICET)
spelling Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2Robles, Norma LisCutin, Edgardo HugoAlvarez, Rosa Maria SusanaOberhammer, HeinzComputational ChemistryConformational PropertiesN-(Chloroformyl) Iminosulfur DichlorideVibrational Spectrahttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1Vibrational spectra [FT IR (gas and liquid); FT Raman (liquid)] and quantum chemical calculations at different levels of theory (HF, B3LYP and MP2 using 6-31G(d), 6-311 + G(2df) and cc-pVTZ base sets) demonstrate that N-(chloroformyl) iminosulfur dichloride (ClC(O)NSCl2) is present in the fluid phases as a mixture of syn–syn and syn–anti forms (syn orientation of the CN bond with respect to the ClSCl bisector; syn or anti orientation of the carbonyl group with respect to the NS bond). From the relative IR intensities of the CO stretching bands the contribution of the syn-anti form is calculated to be 6(2)% in the gas, corresponding to a Gibbs free energy difference ΔG° = G°syn–anti − G°syn–syn = 1.6(3) kcal/mol. This value is reproduced very well by quantum chemical calculations which include electron correlation effects (ΔG° = 1.59–1.91 kcal/mol). The HF approximation overestimates this energy difference (ΔG° = 4.45 kcal/mol). On the basis of theoretical calculations and reported data for other iminosulfur dichlorides, a complete assignment of the fundamental modes for ClC(O)NSCl2 is proposed.Fil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Alvarez, Rosa Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; ArgentinaFil: Oberhammer, Heinz. Universität Tübingen; AlemaniaElsevier Science2008-11info: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/11336/54509Robles, Norma Lis; Cutin, Edgardo Hugo; Alvarez, Rosa Maria Susana; Oberhammer, Heinz; Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2; Elsevier Science; Journal of Molecular Structure; 891; 1-3; 11-2008; 40-440022-2860CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2008.02.036info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286008001543info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:47:28Zoai:ri.conicet.gov.ar:11336/54509instacron: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 09:47:29.017CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
title Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
spellingShingle Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
Robles, Norma Lis
Computational Chemistry
Conformational Properties
N-(Chloroformyl) Iminosulfur Dichloride
Vibrational Spectra
title_short Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
title_full Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
title_fullStr Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
title_full_unstemmed Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
title_sort Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2
dc.creator.none.fl_str_mv Robles, Norma Lis
Cutin, Edgardo Hugo
Alvarez, Rosa Maria Susana
Oberhammer, Heinz
author Robles, Norma Lis
author_facet Robles, Norma Lis
Cutin, Edgardo Hugo
Alvarez, Rosa Maria Susana
Oberhammer, Heinz
author_role author
author2 Cutin, Edgardo Hugo
Alvarez, Rosa Maria Susana
Oberhammer, Heinz
author2_role author
author
author
dc.subject.none.fl_str_mv Computational Chemistry
Conformational Properties
N-(Chloroformyl) Iminosulfur Dichloride
Vibrational Spectra
topic Computational Chemistry
Conformational Properties
N-(Chloroformyl) Iminosulfur Dichloride
Vibrational Spectra
purl_subject.fl_str_mv https://purl.org/becyt/ford/1.4
https://purl.org/becyt/ford/1
dc.description.none.fl_txt_mv Vibrational spectra [FT IR (gas and liquid); FT Raman (liquid)] and quantum chemical calculations at different levels of theory (HF, B3LYP and MP2 using 6-31G(d), 6-311 + G(2df) and cc-pVTZ base sets) demonstrate that N-(chloroformyl) iminosulfur dichloride (ClC(O)NSCl2) is present in the fluid phases as a mixture of syn–syn and syn–anti forms (syn orientation of the CN bond with respect to the ClSCl bisector; syn or anti orientation of the carbonyl group with respect to the NS bond). From the relative IR intensities of the CO stretching bands the contribution of the syn-anti form is calculated to be 6(2)% in the gas, corresponding to a Gibbs free energy difference ΔG° = G°syn–anti − G°syn–syn = 1.6(3) kcal/mol. This value is reproduced very well by quantum chemical calculations which include electron correlation effects (ΔG° = 1.59–1.91 kcal/mol). The HF approximation overestimates this energy difference (ΔG° = 4.45 kcal/mol). On the basis of theoretical calculations and reported data for other iminosulfur dichlorides, a complete assignment of the fundamental modes for ClC(O)NSCl2 is proposed.
Fil: Robles, Norma Lis. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Cutin, Edgardo Hugo. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Alvarez, Rosa Maria Susana. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Tucumán. Instituto de Química del Noroeste. Universidad Nacional de Tucumán. Facultad de Bioquímica, Química y Farmacia. Instituto de Química del Noroeste; Argentina
Fil: Oberhammer, Heinz. Universität Tübingen; Alemania
description Vibrational spectra [FT IR (gas and liquid); FT Raman (liquid)] and quantum chemical calculations at different levels of theory (HF, B3LYP and MP2 using 6-31G(d), 6-311 + G(2df) and cc-pVTZ base sets) demonstrate that N-(chloroformyl) iminosulfur dichloride (ClC(O)NSCl2) is present in the fluid phases as a mixture of syn–syn and syn–anti forms (syn orientation of the CN bond with respect to the ClSCl bisector; syn or anti orientation of the carbonyl group with respect to the NS bond). From the relative IR intensities of the CO stretching bands the contribution of the syn-anti form is calculated to be 6(2)% in the gas, corresponding to a Gibbs free energy difference ΔG° = G°syn–anti − G°syn–syn = 1.6(3) kcal/mol. This value is reproduced very well by quantum chemical calculations which include electron correlation effects (ΔG° = 1.59–1.91 kcal/mol). The HF approximation overestimates this energy difference (ΔG° = 4.45 kcal/mol). On the basis of theoretical calculations and reported data for other iminosulfur dichlorides, a complete assignment of the fundamental modes for ClC(O)NSCl2 is proposed.
publishDate 2008
dc.date.none.fl_str_mv 2008-11
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/11336/54509
Robles, Norma Lis; Cutin, Edgardo Hugo; Alvarez, Rosa Maria Susana; Oberhammer, Heinz; Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2; Elsevier Science; Journal of Molecular Structure; 891; 1-3; 11-2008; 40-44
0022-2860
CONICET Digital
CONICET
url http://hdl.handle.net/11336/54509
identifier_str_mv Robles, Norma Lis; Cutin, Edgardo Hugo; Alvarez, Rosa Maria Susana; Oberhammer, Heinz; Structure and conformations of N-(chloroformyl) iminosulfur dichloride, ClC(O)=NSCl2; Elsevier Science; Journal of Molecular Structure; 891; 1-3; 11-2008; 40-44
0022-2860
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/doi/10.1016/j.molstruc.2008.02.036
info:eu-repo/semantics/altIdentifier/url/https://www.sciencedirect.com/science/article/pii/S0022286008001543
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 Elsevier Science
publisher.none.fl_str_mv Elsevier Science
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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