Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides

Autores
Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto
Año de publicación
2017
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The products following Cl atom initiated reactions of FC(O)OOC(O)OCH3 in 50-760 Torr of N2 at 296 K were investigated using FTIR. Reaction of Cl atoms with methyl fluoroformyl peroxycarbonate proceeds mainly via attack at the methyl group, forming FC(O)OOC(O)OCH2 • radicals. Further reaction of this kind of radical with Cl2 forms three new compounds: FC(O)OOC(O)OCH2Cl, FC(O)OOC(O)OCHCl2, and FC(O)OOC(O)OCCl3, whose existence was characterized experimentally by FTIR spectroscopy assisted by ab initio calculations at the B3LYP/6-31++G(d,p) level. Relative rate techniques were used to measure k(Cl+FC(O)OOC(O)OCH3) = (4.0 ± 0.4) × 10-14 cm3 molecule-1 s-1 and k(Cl+FC(O)OOC(O)OCH2Cl) = (3.2 ± 0.3) × 10-14 cm3 molecule-1 s-1. When the reaction is run in the presence of oxygen, the paths giving chlorinated peroxide formation are suppressed, and oxidation to (mainly) CO2 and HCl takes place through highly oxidized intermediates with lifetimes long enough to be detected by FTIR spectroscopy.
Fil: Berasategui, Matias. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Argüello, Gustavo Alejandro. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Burgos Paci, Maximiliano Alberto. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Materia
Fotochemistry
Ftir Spectroscopy
Laser
Radicals
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:11336/63991
Acceder
id CONICETDig_70ee41ed8ee4eb80ea21a03c5baf6d59
oai_identifier_str oai:ri.conicet.gov.ar:11336/63991
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxidesBerasategui, MatiasArgüello, Gustavo AlejandroBurgos Paci, Maximiliano AlbertoFotochemistryFtir SpectroscopyLaserRadicalshttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The products following Cl atom initiated reactions of FC(O)OOC(O)OCH3 in 50-760 Torr of N2 at 296 K were investigated using FTIR. Reaction of Cl atoms with methyl fluoroformyl peroxycarbonate proceeds mainly via attack at the methyl group, forming FC(O)OOC(O)OCH2 • radicals. Further reaction of this kind of radical with Cl2 forms three new compounds: FC(O)OOC(O)OCH2Cl, FC(O)OOC(O)OCHCl2, and FC(O)OOC(O)OCCl3, whose existence was characterized experimentally by FTIR spectroscopy assisted by ab initio calculations at the B3LYP/6-31++G(d,p) level. Relative rate techniques were used to measure k(Cl+FC(O)OOC(O)OCH3) = (4.0 ± 0.4) × 10-14 cm3 molecule-1 s-1 and k(Cl+FC(O)OOC(O)OCH2Cl) = (3.2 ± 0.3) × 10-14 cm3 molecule-1 s-1. When the reaction is run in the presence of oxygen, the paths giving chlorinated peroxide formation are suppressed, and oxidation to (mainly) CO2 and HCl takes place through highly oxidized intermediates with lifetimes long enough to be detected by FTIR spectroscopy.Fil: Berasategui, Matias. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Argüello, Gustavo Alejandro. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaFil: Burgos Paci, Maximiliano Alberto. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; ArgentinaAmerican Chemical Society2017-10-20info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/63991Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto; Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides; American Chemical Society; Journal of Physical Chemistry A; 121; 40; 20-10-2017; 7469–74761089-56391520-5215CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b07449info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.7b07449info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-10-15T14:39:39Zoai:ri.conicet.gov.ar:11336/63991instacron: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:34982025-10-15 14:39:40.228CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides
title Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides
spellingShingle Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides
Berasategui, Matias
Fotochemistry
Ftir Spectroscopy
Laser
Radicals
title_short Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides
title_full Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides
title_fullStr Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides
title_full_unstemmed Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides
title_sort Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides
dc.creator.none.fl_str_mv Berasategui, Matias
Argüello, Gustavo Alejandro
Burgos Paci, Maximiliano Alberto
author Berasategui, Matias
author_facet Berasategui, Matias
Argüello, Gustavo Alejandro
Burgos Paci, Maximiliano Alberto
author_role author
author2 Argüello, Gustavo Alejandro
Burgos Paci, Maximiliano Alberto
author2_role author
author
dc.subject.none.fl_str_mv Fotochemistry
Ftir Spectroscopy
Laser
Radicals
topic Fotochemistry
Ftir Spectroscopy
Laser
Radicals
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 products following Cl atom initiated reactions of FC(O)OOC(O)OCH3 in 50-760 Torr of N2 at 296 K were investigated using FTIR. Reaction of Cl atoms with methyl fluoroformyl peroxycarbonate proceeds mainly via attack at the methyl group, forming FC(O)OOC(O)OCH2 • radicals. Further reaction of this kind of radical with Cl2 forms three new compounds: FC(O)OOC(O)OCH2Cl, FC(O)OOC(O)OCHCl2, and FC(O)OOC(O)OCCl3, whose existence was characterized experimentally by FTIR spectroscopy assisted by ab initio calculations at the B3LYP/6-31++G(d,p) level. Relative rate techniques were used to measure k(Cl+FC(O)OOC(O)OCH3) = (4.0 ± 0.4) × 10-14 cm3 molecule-1 s-1 and k(Cl+FC(O)OOC(O)OCH2Cl) = (3.2 ± 0.3) × 10-14 cm3 molecule-1 s-1. When the reaction is run in the presence of oxygen, the paths giving chlorinated peroxide formation are suppressed, and oxidation to (mainly) CO2 and HCl takes place through highly oxidized intermediates with lifetimes long enough to be detected by FTIR spectroscopy.
Fil: Berasategui, Matias. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Argüello, Gustavo Alejandro. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
Fil: Burgos Paci, Maximiliano Alberto. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Departamento de Fisicoquímica; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Córdoba. Instituto de Investigaciones en Físico-química de Córdoba. Universidad Nacional de Córdoba. Facultad de Ciencias Químicas. Instituto de Investigaciones en Físico-química de Córdoba; Argentina
description The products following Cl atom initiated reactions of FC(O)OOC(O)OCH3 in 50-760 Torr of N2 at 296 K were investigated using FTIR. Reaction of Cl atoms with methyl fluoroformyl peroxycarbonate proceeds mainly via attack at the methyl group, forming FC(O)OOC(O)OCH2 • radicals. Further reaction of this kind of radical with Cl2 forms three new compounds: FC(O)OOC(O)OCH2Cl, FC(O)OOC(O)OCHCl2, and FC(O)OOC(O)OCCl3, whose existence was characterized experimentally by FTIR spectroscopy assisted by ab initio calculations at the B3LYP/6-31++G(d,p) level. Relative rate techniques were used to measure k(Cl+FC(O)OOC(O)OCH3) = (4.0 ± 0.4) × 10-14 cm3 molecule-1 s-1 and k(Cl+FC(O)OOC(O)OCH2Cl) = (3.2 ± 0.3) × 10-14 cm3 molecule-1 s-1. When the reaction is run in the presence of oxygen, the paths giving chlorinated peroxide formation are suppressed, and oxidation to (mainly) CO2 and HCl takes place through highly oxidized intermediates with lifetimes long enough to be detected by FTIR spectroscopy.
publishDate 2017
dc.date.none.fl_str_mv 2017-10-20
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/11336/63991
Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto; Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides; American Chemical Society; Journal of Physical Chemistry A; 121; 40; 20-10-2017; 7469–7476
1089-5639
1520-5215
CONICET Digital
CONICET
url http://hdl.handle.net/11336/63991
identifier_str_mv Berasategui, Matias; Argüello, Gustavo Alejandro; Burgos Paci, Maximiliano Alberto; Reaction of methyl fluoroformyl peroxycarbonate (FC(O)OOC(O)OCH3) with Cl atoms: Formation of hydro-chlorofluoro-peroxides; American Chemical Society; Journal of Physical Chemistry A; 121; 40; 20-10-2017; 7469–7476
1089-5639
1520-5215
CONICET Digital
CONICET
dc.language.none.fl_str_mv eng
language eng
dc.relation.none.fl_str_mv info:eu-repo/semantics/altIdentifier/url/http://pubs.acs.org/doi/abs/10.1021/acs.jpca.7b07449
info:eu-repo/semantics/altIdentifier/doi/10.1021/acs.jpca.7b07449
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
_version_ 1846082883471540224
score 13.22299

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