Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)

Autores
Gutiérrez, María M.; Olabe Iparraguirre, Jose Antonio; Amorebieta, Valentín Tomás
Año de publicación
2011
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The aquapentacyanoferrate(II) ion, [FeII(CN)5H2O]3-, catalyzes the disproportionation reaction of O-methylhydroxylamine, NH2OCH3, with stoichiometry 3 NH2OCH3 ==0 NH3 + N2 + 3 CH3OH. Kinetic and spectroscopic evidence support an initial N coordination of NH2OCH3 to [FeII(CN)5H2O]3- followed by a homolytic scission leading to radicals [FeII(CN)5•NH2]3- (a precursor of Fe(III) centers and bound NH3) and free methoxyl, CH3O•, thus establishing a radical path leading to N-methoxyamino (•NHOCH3) and 1,2-dimethoxyhydrazine, (NHOCH3)2. The latter species is moderately stable and proposed to be the precursor of N2 and most of the generated CH3OH. Intermediate [FeIII(CN)5L]2- complexes (L = NH3, H2O) form dinuclear cyano-bridged mixed-valent species, affording a catalytic substitution of the L ligands promoted by [FeII(CN)5L]3-. Free or bound NH2OCH3 may act as reductants of [FeIII(CN)5L]2-, thus regenerating active sites. At increasing concentrations of NH2OCH3 a coordinated diazene species emerges, [FeII(CN)5N2H2]3-, which is consumed by the oxidizing CH3O•, giving N2 and CH3OH. Another side reaction forms [FeII(CN)5N(O)CH3]3-, an intermediate containing the nitrosomethane ligand, which is further oxidized to the nitroprusside ion, [FeII(CN)5NO]2-. The latter is a final oxidation product with a significant conversion of the initial [FeII(CN)5H2O]3- complex. The side reaction partially blocks the Fe(II)aqua active site, though complete inhibition is not achieved because the radical path evolves faster than the formation rates of the FeIINO+ bonds.
Fil: Gutiérrez, María M.. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales; Argentina
Fil: Olabe Iparraguirre, Jose Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Amorebieta, Valentín Tomás. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina
Materia
O-METHYLHYDROXYLAMINE
PENTACYANOFERRATES
DISPROPORTIONATION
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:11336/278605
Acceder
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oai_identifier_str oai:ri.conicet.gov.ar:11336/278605
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)Gutiérrez, María M.Olabe Iparraguirre, Jose AntonioAmorebieta, Valentín TomásO-METHYLHYDROXYLAMINEPENTACYANOFERRATESDISPROPORTIONATIONhttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The aquapentacyanoferrate(II) ion, [FeII(CN)5H2O]3-, catalyzes the disproportionation reaction of O-methylhydroxylamine, NH2OCH3, with stoichiometry 3 NH2OCH3 ==0 NH3 + N2 + 3 CH3OH. Kinetic and spectroscopic evidence support an initial N coordination of NH2OCH3 to [FeII(CN)5H2O]3- followed by a homolytic scission leading to radicals [FeII(CN)5•NH2]3- (a precursor of Fe(III) centers and bound NH3) and free methoxyl, CH3O•, thus establishing a radical path leading to N-methoxyamino (•NHOCH3) and 1,2-dimethoxyhydrazine, (NHOCH3)2. The latter species is moderately stable and proposed to be the precursor of N2 and most of the generated CH3OH. Intermediate [FeIII(CN)5L]2- complexes (L = NH3, H2O) form dinuclear cyano-bridged mixed-valent species, affording a catalytic substitution of the L ligands promoted by [FeII(CN)5L]3-. Free or bound NH2OCH3 may act as reductants of [FeIII(CN)5L]2-, thus regenerating active sites. At increasing concentrations of NH2OCH3 a coordinated diazene species emerges, [FeII(CN)5N2H2]3-, which is consumed by the oxidizing CH3O•, giving N2 and CH3OH. Another side reaction forms [FeII(CN)5N(O)CH3]3-, an intermediate containing the nitrosomethane ligand, which is further oxidized to the nitroprusside ion, [FeII(CN)5NO]2-. The latter is a final oxidation product with a significant conversion of the initial [FeII(CN)5H2O]3- complex. The side reaction partially blocks the Fe(II)aqua active site, though complete inhibition is not achieved because the radical path evolves faster than the formation rates of the FeIINO+ bonds.Fil: Gutiérrez, María M.. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales; ArgentinaFil: Olabe Iparraguirre, Jose Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; ArgentinaFil: Amorebieta, Valentín Tomás. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; ArgentinaAmerican Chemical Society2011-09info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/pdfapplication/pdfhttp://hdl.handle.net/11336/278605Gutiérrez, María M.; Olabe Iparraguirre, Jose Antonio; Amorebieta, Valentín Tomás; Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II); American Chemical Society; Inorganic Chemistry; 50; 18; 9-2011; 8817-88250020-1669CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.acs.org/doi/10.1021/ic2007155info:eu-repo/semantics/altIdentifier/doi/10.1021/ic2007155info:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2026-02-06T12:43:13Zoai:ri.conicet.gov.ar:11336/278605instacron: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:34982026-02-06 12:43:13.601CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)
title Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)
spellingShingle Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)
Gutiérrez, María M.
O-METHYLHYDROXYLAMINE
PENTACYANOFERRATES
DISPROPORTIONATION
title_short Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)
title_full Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)
title_fullStr Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)
title_full_unstemmed Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)
title_sort Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II)
dc.creator.none.fl_str_mv Gutiérrez, María M.
Olabe Iparraguirre, Jose Antonio
Amorebieta, Valentín Tomás
author Gutiérrez, María M.
author_facet Gutiérrez, María M.
Olabe Iparraguirre, Jose Antonio
Amorebieta, Valentín Tomás
author_role author
author2 Olabe Iparraguirre, Jose Antonio
Amorebieta, Valentín Tomás
author2_role author
author
dc.subject.none.fl_str_mv O-METHYLHYDROXYLAMINE
PENTACYANOFERRATES
DISPROPORTIONATION
topic O-METHYLHYDROXYLAMINE
PENTACYANOFERRATES
DISPROPORTIONATION
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 aquapentacyanoferrate(II) ion, [FeII(CN)5H2O]3-, catalyzes the disproportionation reaction of O-methylhydroxylamine, NH2OCH3, with stoichiometry 3 NH2OCH3 ==0 NH3 + N2 + 3 CH3OH. Kinetic and spectroscopic evidence support an initial N coordination of NH2OCH3 to [FeII(CN)5H2O]3- followed by a homolytic scission leading to radicals [FeII(CN)5•NH2]3- (a precursor of Fe(III) centers and bound NH3) and free methoxyl, CH3O•, thus establishing a radical path leading to N-methoxyamino (•NHOCH3) and 1,2-dimethoxyhydrazine, (NHOCH3)2. The latter species is moderately stable and proposed to be the precursor of N2 and most of the generated CH3OH. Intermediate [FeIII(CN)5L]2- complexes (L = NH3, H2O) form dinuclear cyano-bridged mixed-valent species, affording a catalytic substitution of the L ligands promoted by [FeII(CN)5L]3-. Free or bound NH2OCH3 may act as reductants of [FeIII(CN)5L]2-, thus regenerating active sites. At increasing concentrations of NH2OCH3 a coordinated diazene species emerges, [FeII(CN)5N2H2]3-, which is consumed by the oxidizing CH3O•, giving N2 and CH3OH. Another side reaction forms [FeII(CN)5N(O)CH3]3-, an intermediate containing the nitrosomethane ligand, which is further oxidized to the nitroprusside ion, [FeII(CN)5NO]2-. The latter is a final oxidation product with a significant conversion of the initial [FeII(CN)5H2O]3- complex. The side reaction partially blocks the Fe(II)aqua active site, though complete inhibition is not achieved because the radical path evolves faster than the formation rates of the FeIINO+ bonds.
Fil: Gutiérrez, María M.. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales; Argentina
Fil: Olabe Iparraguirre, Jose Antonio. Consejo Nacional de Investigaciones Científicas y Técnicas. Oficina de Coordinación Administrativa Ciudad Universitaria. Instituto de Química, Física de los Materiales, Medioambiente y Energía. Universidad de Buenos Aires. Facultad de Ciencias Exactas y Naturales. Instituto de Química, Física de los Materiales, Medioambiente y Energía; Argentina
Fil: Amorebieta, Valentín Tomás. Universidad Nacional de Mar del Plata. Facultad de Ciencias Exactas y Naturales; Argentina. Consejo Nacional de Investigaciones Científicas y Técnicas. Centro Científico Tecnológico Conicet - Mar del Plata; Argentina
description The aquapentacyanoferrate(II) ion, [FeII(CN)5H2O]3-, catalyzes the disproportionation reaction of O-methylhydroxylamine, NH2OCH3, with stoichiometry 3 NH2OCH3 ==0 NH3 + N2 + 3 CH3OH. Kinetic and spectroscopic evidence support an initial N coordination of NH2OCH3 to [FeII(CN)5H2O]3- followed by a homolytic scission leading to radicals [FeII(CN)5•NH2]3- (a precursor of Fe(III) centers and bound NH3) and free methoxyl, CH3O•, thus establishing a radical path leading to N-methoxyamino (•NHOCH3) and 1,2-dimethoxyhydrazine, (NHOCH3)2. The latter species is moderately stable and proposed to be the precursor of N2 and most of the generated CH3OH. Intermediate [FeIII(CN)5L]2- complexes (L = NH3, H2O) form dinuclear cyano-bridged mixed-valent species, affording a catalytic substitution of the L ligands promoted by [FeII(CN)5L]3-. Free or bound NH2OCH3 may act as reductants of [FeIII(CN)5L]2-, thus regenerating active sites. At increasing concentrations of NH2OCH3 a coordinated diazene species emerges, [FeII(CN)5N2H2]3-, which is consumed by the oxidizing CH3O•, giving N2 and CH3OH. Another side reaction forms [FeII(CN)5N(O)CH3]3-, an intermediate containing the nitrosomethane ligand, which is further oxidized to the nitroprusside ion, [FeII(CN)5NO]2-. The latter is a final oxidation product with a significant conversion of the initial [FeII(CN)5H2O]3- complex. The side reaction partially blocks the Fe(II)aqua active site, though complete inhibition is not achieved because the radical path evolves faster than the formation rates of the FeIINO+ bonds.
publishDate 2011
dc.date.none.fl_str_mv 2011-09
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/11336/278605
Gutiérrez, María M.; Olabe Iparraguirre, Jose Antonio; Amorebieta, Valentín Tomás; Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II); American Chemical Society; Inorganic Chemistry; 50; 18; 9-2011; 8817-8825
0020-1669
CONICET Digital
CONICET
url http://hdl.handle.net/11336/278605
identifier_str_mv Gutiérrez, María M.; Olabe Iparraguirre, Jose Antonio; Amorebieta, Valentín Tomás; Disproportionation of O -Methylhydroxylamine Catalyzed by Aquapentacyanoferrate(II); American Chemical Society; Inorganic Chemistry; 50; 18; 9-2011; 8817-8825
0020-1669
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/ic2007155
info:eu-repo/semantics/altIdentifier/doi/10.1021/ic2007155
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
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 13.106097

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