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Abstract:

The kinetics of the reaction between aqueous solutions of [Fe(CN) 5NO] 2- and NH 2OCH 3 has been studied by means of UV/Vis spectroscopy and complementary solution techniques, FTIR/ATR spectroscopy, mass spectrometry, and isotopic labeling ([Fe(CN) 5 15NO] 2-), in the pH range 6.0-9.3, I = 1 M (NaCl). The main products were nitrous oxide (N 15NO), CH 3OH, and [Fe II(CN) 5H 2O] 3-, characterized as the [Fe II(CN) 5(pyCONH 2)] 3- complex (pyCONH 2 = isonicotinamide). In excess NH 2OCH 3, the kinetic runs indicated pseudo-first-order behavior, with corresponding rate constants, k obs [s -1], that correlated linearly with the concentration of NH 2OCH 3. The rate law is: R = k exp[Fe(CN) 5NO 2-][NH 2OCH 3], with k exp = (4.1 ± 0.4) × 10 -4 M -1 s -1 at 25 ± 0.2 °C, ΔH # = 27 ± 1 kJ mol -1, and ΔS # = -220 ± 5 J K -1 mol -1, at pH 7.1. The value of k exp is much lower than that for similar addition reactions of NH 2OH and of the N-substituted methyl derivative. In addition, the latter reactions exhibit a third-order rate law with a linear dependence of R on the concentration of OH -. The reaction profile has been modeled by density functional theoretical methodologies, providing mechanistic evidence on the different reaction steps, namely, the adduct formation and subsequent decomposition processes, with valuable comparisons with the reactivity of other nucleophiles with [Fe(CN) 5NO] 2-. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

Registro:

Documento: Artículo
Título:Nucleophilic addition reactions of the nitroprusside ion - The case of O-methylhydroxylamine
Autor:Gutiérrez, M.M.; 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, INQUIMAE/CONICET, Ciudad Universitaria, Pabellón 2, Buenos Aires C1428EHA, Argentina
Palabras clave:Amines; Density functional calculations; Iron; Kinetics; Nucleophilic addition
Año:2012
Número:28
Página de inicio:4433
Página de fin:4438
DOI: http://dx.doi.org/10.1002/ejic.201200387
Título revista:European Journal of Inorganic Chemistry
Título revista abreviado:Eur. J. Inorg. Chem.
ISSN:14341948
CODEN:EJICF
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_14341948_v_n28_p4433_Gutierrez

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Citas:

---------- APA ----------
Gutiérrez, M.M., Olabe, J.A. & Amorebieta, V.T. (2012) . Nucleophilic addition reactions of the nitroprusside ion - The case of O-methylhydroxylamine. European Journal of Inorganic Chemistry(28), 4433-4438.
http://dx.doi.org/10.1002/ejic.201200387
---------- CHICAGO ----------
Gutiérrez, M.M., Olabe, J.A., Amorebieta, V.T. "Nucleophilic addition reactions of the nitroprusside ion - The case of O-methylhydroxylamine" . European Journal of Inorganic Chemistry, no. 28 (2012) : 4433-4438.
http://dx.doi.org/10.1002/ejic.201200387
---------- MLA ----------
Gutiérrez, M.M., Olabe, J.A., Amorebieta, V.T. "Nucleophilic addition reactions of the nitroprusside ion - The case of O-methylhydroxylamine" . European Journal of Inorganic Chemistry, no. 28, 2012, pp. 4433-4438.
http://dx.doi.org/10.1002/ejic.201200387
---------- VANCOUVER ----------
Gutiérrez, M.M., Olabe, J.A., Amorebieta, V.T. Nucleophilic addition reactions of the nitroprusside ion - The case of O-methylhydroxylamine. Eur. J. Inorg. Chem. 2012(28):4433-4438.
http://dx.doi.org/10.1002/ejic.201200387