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Abstract:

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. © The Royal Society of Chemistry 2008.

Registro:

Documento: Artículo
Título:Nitrosation of N-methylhydroxylamine by nitroprusside. A kinetic and mechanistic study
Autor:Gutiérrez, M.M.; Alluisetti, G.B.; Olabe, J.A.; Amorebieta, V.T.
Filiación:Department of Chemistry, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar Del Plata, Funes y Roca, Mar del Plata B7602AYL, Argentina
Department of Inorganic, Analytical and Physical Chemistry, Facultad de Ciencias Exactas y Naturales, Ciudad Universitaria, Pabellón 2, C1428EHA, Buenos Aires, Argentina
Palabras clave:Chemical reactions; Reaction kinetics; Sodium; Aqueous solutions; Mechanistic studies; Nitrosation; Solutions; hydroxylamine; n methylhydroxylamine; N-methylhydroxylamine; nitroprusside sodium; article; chemical model; chemistry; electron spin resonance; infrared spectroscopy; kinetics; mass spectrometry; methodology; nitrosation; pH; time; ultraviolet spectrophotometry; Electron Spin Resonance Spectroscopy; Hydrogen-Ion Concentration; Hydroxylamines; Kinetics; Mass Spectrometry; Models, Chemical; Nitroprusside; Nitrosation; Spectrophotometry, Ultraviolet; Spectroscopy, Fourier Transform Infrared; Time Factors
Año:2008
Número:37
Página de inicio:5025
Página de fin:5030
DOI: http://dx.doi.org/10.1039/b805329d
Título revista:Dalton Transactions
Título revista abreviado:Dalton Trans.
ISSN:14779226
CAS:hydroxylamine, 7803-49-8; n methylhydroxylamine, 593-77-1; nitroprusside sodium, 14402-89-2, 15078-28-1; Hydroxylamines; N-methylhydroxylamine, 593-77-1; Nitroprusside, 15078-28-1
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14779226_v_n37_p5025_Gutierrez

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Citas:

---------- APA ----------
Gutiérrez, M.M., Alluisetti, G.B., Olabe, J.A. & Amorebieta, V.T. (2008) . Nitrosation of N-methylhydroxylamine by nitroprusside. A kinetic and mechanistic study. Dalton Transactions(37), 5025-5030.
http://dx.doi.org/10.1039/b805329d
---------- CHICAGO ----------
Gutiérrez, M.M., Alluisetti, G.B., Olabe, J.A., Amorebieta, V.T. "Nitrosation of N-methylhydroxylamine by nitroprusside. A kinetic and mechanistic study" . Dalton Transactions, no. 37 (2008) : 5025-5030.
http://dx.doi.org/10.1039/b805329d
---------- MLA ----------
Gutiérrez, M.M., Alluisetti, G.B., Olabe, J.A., Amorebieta, V.T. "Nitrosation of N-methylhydroxylamine by nitroprusside. A kinetic and mechanistic study" . Dalton Transactions, no. 37, 2008, pp. 5025-5030.
http://dx.doi.org/10.1039/b805329d
---------- VANCOUVER ----------
Gutiérrez, M.M., Alluisetti, G.B., Olabe, J.A., Amorebieta, V.T. Nitrosation of N-methylhydroxylamine by nitroprusside. A kinetic and mechanistic study. Dalton Trans. 2008(37):5025-5030.
http://dx.doi.org/10.1039/b805329d