Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study

Autores
Gutierrez, Maria Marta; Alluisetti, Graciela Beatriz; Olabe Iparraguirre, Jose Antonio; Amorebieta, Valentín Tomás
Año de publicación
2008
Idioma
inglés
Tipo de recurso
artículo
Estado
versión publicada
Descripción
The kinetics of the reaction between aqueous solutions of Na 2[Fe(CN)5NO]•2H2O (sodium pentacyanonitrosylferrate(ii), nitroprusside, SNP) and MeN(H)OH (N-methylhydroxylamine, MeHA) has been studied by means of UV-vis spectroscopy, using complementary solution techniques: FTIR/ATR, EPR, mass spectrometry and isotopic labeling (15NO), in the pH range 7.1-9.3, I = 1 M (NaCl). The main products were N-methyl-N-nitrosohydroxylamine (MeN(NO)OH) and [Fe(CN)5H2O]3-, characterized as the [Fe(CN)5(pyCONH2)]3- complex (pyCONH 2 = isonicotinamide). No reaction occurred with Me2NOH (N,N-dimethylhydroxylamine, Me2HA) as nucleophile. The rate law was: R = kexp [Fe(CN)5NO2-] × [MeN(H)OH] × [OH-], with kexp = 1.6 ± 0.2 × 105 M-2 s-1, at 25.0 °C, and ΔH # = 34 ± 3 kJ mol-1, ΔS# = -32 ± 11 J K-1 mol-1, at pH 8.0. The proposed mechanism involves the formation of a precursor associative complex between SNP and MeHA, followed by an OH--assisted reversible formation of a deprotonated adduct, [Fe(CN)5(N(O)NMeOH)]3-, and rapid dissociation of MeN(NO)OH. In excess SNP, the precursor complex reacts through a competitive one-electron-transfer path, forming the [Fe(CN)5NO]3- ion with slow production of small quantities of N2O. The stoichiometry and mechanism of the main adduct-formation path are similar to those previously reported for hydroxylamine (HA) and related nucleophiles. The nitrosated product, MeN(NO)OH, decomposes thermally at physiological temperatures, slowly yielding NO.
Fil: Gutierrez, Maria Marta. Universidad Nacional de Mar del Plata; Argentina
Fil: Alluisetti, Graciela Beatriz. Universidad Nacional de Mar del Plata; 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; Argentina
Materia
Nitrosation
Methylhydroxylamine
Nitroprusside
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:11336/73246
Acceder
id CONICETDig_87fcdab780d5f8ec82216fb392cdc655
oai_identifier_str oai:ri.conicet.gov.ar:11336/73246
network_acronym_str CONICETDig
repository_id_str 3498
network_name_str CONICET Digital (CONICET)
spelling Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic studyGutierrez, Maria MartaAlluisetti, Graciela BeatrizOlabe Iparraguirre, Jose AntonioAmorebieta, Valentín TomásNitrosationMethylhydroxylamineNitroprussidehttps://purl.org/becyt/ford/1.4https://purl.org/becyt/ford/1The kinetics of the reaction between aqueous solutions of Na 2[Fe(CN)5NO]•2H2O (sodium pentacyanonitrosylferrate(ii), nitroprusside, SNP) and MeN(H)OH (N-methylhydroxylamine, MeHA) has been studied by means of UV-vis spectroscopy, using complementary solution techniques: FTIR/ATR, EPR, mass spectrometry and isotopic labeling (15NO), in the pH range 7.1-9.3, I = 1 M (NaCl). The main products were N-methyl-N-nitrosohydroxylamine (MeN(NO)OH) and [Fe(CN)5H2O]3-, characterized as the [Fe(CN)5(pyCONH2)]3- complex (pyCONH 2 = isonicotinamide). No reaction occurred with Me2NOH (N,N-dimethylhydroxylamine, Me2HA) as nucleophile. The rate law was: R = kexp [Fe(CN)5NO2-] × [MeN(H)OH] × [OH-], with kexp = 1.6 ± 0.2 × 105 M-2 s-1, at 25.0 °C, and ΔH # = 34 ± 3 kJ mol-1, ΔS# = -32 ± 11 J K-1 mol-1, at pH 8.0. The proposed mechanism involves the formation of a precursor associative complex between SNP and MeHA, followed by an OH--assisted reversible formation of a deprotonated adduct, [Fe(CN)5(N(O)NMeOH)]3-, and rapid dissociation of MeN(NO)OH. In excess SNP, the precursor complex reacts through a competitive one-electron-transfer path, forming the [Fe(CN)5NO]3- ion with slow production of small quantities of N2O. The stoichiometry and mechanism of the main adduct-formation path are similar to those previously reported for hydroxylamine (HA) and related nucleophiles. The nitrosated product, MeN(NO)OH, decomposes thermally at physiological temperatures, slowly yielding NO.Fil: Gutierrez, Maria Marta. Universidad Nacional de Mar del Plata; ArgentinaFil: Alluisetti, Graciela Beatriz. Universidad Nacional de Mar del Plata; 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; ArgentinaRoyal Society of Chemistry2008-12info:eu-repo/semantics/articleinfo:eu-repo/semantics/publishedVersionhttp://purl.org/coar/resource_type/c_6501info:ar-repo/semantics/articuloapplication/pdfapplication/mswordapplication/pdfhttp://hdl.handle.net/11336/73246Gutierrez, Maria Marta; Alluisetti, Graciela Beatriz; Olabe Iparraguirre, Jose Antonio; Amorebieta, Valentín Tomás; Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study; Royal Society of Chemistry; Dalton Transactions; 37; 12-2008; 5025-50301477-9226CONICET DigitalCONICETenginfo:eu-repo/semantics/altIdentifier/url/https://pubs.rsc.org/en/Content/ArticleLanding/2008/DT/b805329d#!divAbstractinfo:eu-repo/semantics/altIdentifier/doi/10.1039/b805329dinfo:eu-repo/semantics/openAccesshttps://creativecommons.org/licenses/by-nc-sa/2.5/ar/reponame:CONICET Digital (CONICET)instname:Consejo Nacional de Investigaciones Científicas y Técnicas2025-09-03T09:54:21Zoai:ri.conicet.gov.ar:11336/73246instacron: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 09:54:22.044CONICET Digital (CONICET) - Consejo Nacional de Investigaciones Científicas y Técnicasfalse
dc.title.none.fl_str_mv Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study
title Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study
spellingShingle Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study
Gutierrez, Maria Marta
Nitrosation
Methylhydroxylamine
Nitroprusside
title_short Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study
title_full Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study
title_fullStr Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study
title_full_unstemmed Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study
title_sort Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study
dc.creator.none.fl_str_mv Gutierrez, Maria Marta
Alluisetti, Graciela Beatriz
Olabe Iparraguirre, Jose Antonio
Amorebieta, Valentín Tomás
author Gutierrez, Maria Marta
author_facet Gutierrez, Maria Marta
Alluisetti, Graciela Beatriz
Olabe Iparraguirre, Jose Antonio
Amorebieta, Valentín Tomás
author_role author
author2 Alluisetti, Graciela Beatriz
Olabe Iparraguirre, Jose Antonio
Amorebieta, Valentín Tomás
author2_role author
author
author
dc.subject.none.fl_str_mv Nitrosation
Methylhydroxylamine
Nitroprusside
topic Nitrosation
Methylhydroxylamine
Nitroprusside
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 kinetics of the reaction between aqueous solutions of Na 2[Fe(CN)5NO]•2H2O (sodium pentacyanonitrosylferrate(ii), nitroprusside, SNP) and MeN(H)OH (N-methylhydroxylamine, MeHA) has been studied by means of UV-vis spectroscopy, using complementary solution techniques: FTIR/ATR, EPR, mass spectrometry and isotopic labeling (15NO), in the pH range 7.1-9.3, I = 1 M (NaCl). The main products were N-methyl-N-nitrosohydroxylamine (MeN(NO)OH) and [Fe(CN)5H2O]3-, characterized as the [Fe(CN)5(pyCONH2)]3- complex (pyCONH 2 = isonicotinamide). No reaction occurred with Me2NOH (N,N-dimethylhydroxylamine, Me2HA) as nucleophile. The rate law was: R = kexp [Fe(CN)5NO2-] × [MeN(H)OH] × [OH-], with kexp = 1.6 ± 0.2 × 105 M-2 s-1, at 25.0 °C, and ΔH # = 34 ± 3 kJ mol-1, ΔS# = -32 ± 11 J K-1 mol-1, at pH 8.0. The proposed mechanism involves the formation of a precursor associative complex between SNP and MeHA, followed by an OH--assisted reversible formation of a deprotonated adduct, [Fe(CN)5(N(O)NMeOH)]3-, and rapid dissociation of MeN(NO)OH. In excess SNP, the precursor complex reacts through a competitive one-electron-transfer path, forming the [Fe(CN)5NO]3- ion with slow production of small quantities of N2O. The stoichiometry and mechanism of the main adduct-formation path are similar to those previously reported for hydroxylamine (HA) and related nucleophiles. The nitrosated product, MeN(NO)OH, decomposes thermally at physiological temperatures, slowly yielding NO.
Fil: Gutierrez, Maria Marta. Universidad Nacional de Mar del Plata; Argentina
Fil: Alluisetti, Graciela Beatriz. Universidad Nacional de Mar del Plata; 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; Argentina
description The kinetics of the reaction between aqueous solutions of Na 2[Fe(CN)5NO]•2H2O (sodium pentacyanonitrosylferrate(ii), nitroprusside, SNP) and MeN(H)OH (N-methylhydroxylamine, MeHA) has been studied by means of UV-vis spectroscopy, using complementary solution techniques: FTIR/ATR, EPR, mass spectrometry and isotopic labeling (15NO), in the pH range 7.1-9.3, I = 1 M (NaCl). The main products were N-methyl-N-nitrosohydroxylamine (MeN(NO)OH) and [Fe(CN)5H2O]3-, characterized as the [Fe(CN)5(pyCONH2)]3- complex (pyCONH 2 = isonicotinamide). No reaction occurred with Me2NOH (N,N-dimethylhydroxylamine, Me2HA) as nucleophile. The rate law was: R = kexp [Fe(CN)5NO2-] × [MeN(H)OH] × [OH-], with kexp = 1.6 ± 0.2 × 105 M-2 s-1, at 25.0 °C, and ΔH # = 34 ± 3 kJ mol-1, ΔS# = -32 ± 11 J K-1 mol-1, at pH 8.0. The proposed mechanism involves the formation of a precursor associative complex between SNP and MeHA, followed by an OH--assisted reversible formation of a deprotonated adduct, [Fe(CN)5(N(O)NMeOH)]3-, and rapid dissociation of MeN(NO)OH. In excess SNP, the precursor complex reacts through a competitive one-electron-transfer path, forming the [Fe(CN)5NO]3- ion with slow production of small quantities of N2O. The stoichiometry and mechanism of the main adduct-formation path are similar to those previously reported for hydroxylamine (HA) and related nucleophiles. The nitrosated product, MeN(NO)OH, decomposes thermally at physiological temperatures, slowly yielding NO.
publishDate 2008
dc.date.none.fl_str_mv 2008-12
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/11336/73246
Gutierrez, Maria Marta; Alluisetti, Graciela Beatriz; Olabe Iparraguirre, Jose Antonio; Amorebieta, Valentín Tomás; Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study; Royal Society of Chemistry; Dalton Transactions; 37; 12-2008; 5025-5030
1477-9226
CONICET Digital
CONICET
url http://hdl.handle.net/11336/73246
identifier_str_mv Gutierrez, Maria Marta; Alluisetti, Graciela Beatriz; Olabe Iparraguirre, Jose Antonio; Amorebieta, Valentín Tomás; Nitrosation of N-methylhydroxylamine by nitroprusside: a kinetic and mechanistic study; Royal Society of Chemistry; Dalton Transactions; 37; 12-2008; 5025-5030
1477-9226
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.rsc.org/en/Content/ArticleLanding/2008/DT/b805329d#!divAbstract
info:eu-repo/semantics/altIdentifier/doi/10.1039/b805329d
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/msword
application/pdf
dc.publisher.none.fl_str_mv Royal Society of Chemistry
publisher.none.fl_str_mv Royal Society of Chemistry
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_ 1842269281200373760
score 13.13397

Publicaciones similares