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Abstract:

The kinetics and mechanism of the reaction between nitric oxide and aquapentacyanoferrate(III) were studied in detail. Pentacyanonitrosylferrate (nitroprusside, NP) was produced quantitatively in a pseudo-first-order process. The complex-formation rate constant was found to be 0.252 ±0.004 M-1 S-1 at 25.5 °C, pH 3.0 (HCIO4), and l = 0.1 M (NaCIO4), for which the activation parameters are ΔV‡=52±1 kJ mol-1,ΔS‡=-82±4JK-1 mol-1, and ΔV‡=-13.9 + 0.5 cm3 mol-1. These data disagree with earlier studies on complex-formation reactions of aquapentacyanoferrate(III), for which a dissociative interchange (Id mechanism was suggested. The aquapentacyanoferrate(II) ion was detected as a reactive intermediate in the reaction of aquapentacyanoferrate(III) with NO, by using pyrazine and thiocyanate as scavengers for this intermediate. In addition, the reactions of other [FeIII(CN)5L]n- complexes (L = NCS-, py, NO2-, and CN-) with NO were studied. These experiments also pointed to the formation of Fe(II) species as intermediates. It is proposed that aquapentacyanoferrate(III) is reduced by NO to the corresponding Fe(II) complex through a rate-determining outer-sphere electron-transfer reaction controlling the overall processes. The Fe(II) complex rapidly reacts with nitrite producing [FeII(CN)5NO2]4-, followed by the fast and irreversible conversion to NP.

Registro:

Documento: Artículo
Título:Kinetics and mechanism of the formation of nitroprusside from aquapentacyanoferrate(III) and NO: Complex formation controlled by outer-sphere electron transfer
Autor:Roncaroli, F.; Olabe, J.A.; van Eldik, R.
Filiación:Institute of Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany
Department of Inorganic, Analytical and Physical Chemistry, Inquimae, Faculty of Exact and Natural Sciences, University of Buenos Aires, C1428EHA Buenos Aires, Argentina
Palabras clave:aquapentacyanoferrate; dyes, reagents, indicators, markers and buffers; ferric ion; iron derivative; nitric oxide; nitroprusside sodium; pentacyanoferrate (III); pyrazine derivative; scavenger; thiocyanic acid derivative; unclassified drug; algorithm; article; chemical reaction; chemistry; complex formation; dissociation; electron transport; kinetics; oxidation reduction reaction; pH; synthesis; temperature dependence; Algorithms; Electron Transport; Ferric Compounds; Indicators and Reagents; Kinetics; Nitric Oxide; Nitroprusside; Oxidation-Reduction
Año:2002
Volumen:41
Número:21
Página de inicio:5417
Página de fin:5425
DOI: http://dx.doi.org/10.1021/ic020288o
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
CAS:ferric ion, 20074-52-6; nitric oxide, 10102-43-9; nitroprusside sodium, 14402-89-2, 15078-28-1; Ferric Compounds; Indicators and Reagents; Nitric Oxide, 10102-43-9; Nitroprusside, 15078-28-1; pentacyanoferrate (III)
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v41_n21_p5417_Roncaroli

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Citas:

---------- APA ----------
Roncaroli, F., Olabe, J.A. & van Eldik, R. (2002) . Kinetics and mechanism of the formation of nitroprusside from aquapentacyanoferrate(III) and NO: Complex formation controlled by outer-sphere electron transfer. Inorganic Chemistry, 41(21), 5417-5425.
http://dx.doi.org/10.1021/ic020288o
---------- CHICAGO ----------
Roncaroli, F., Olabe, J.A., van Eldik, R. "Kinetics and mechanism of the formation of nitroprusside from aquapentacyanoferrate(III) and NO: Complex formation controlled by outer-sphere electron transfer" . Inorganic Chemistry 41, no. 21 (2002) : 5417-5425.
http://dx.doi.org/10.1021/ic020288o
---------- MLA ----------
Roncaroli, F., Olabe, J.A., van Eldik, R. "Kinetics and mechanism of the formation of nitroprusside from aquapentacyanoferrate(III) and NO: Complex formation controlled by outer-sphere electron transfer" . Inorganic Chemistry, vol. 41, no. 21, 2002, pp. 5417-5425.
http://dx.doi.org/10.1021/ic020288o
---------- VANCOUVER ----------
Roncaroli, F., Olabe, J.A., van Eldik, R. Kinetics and mechanism of the formation of nitroprusside from aquapentacyanoferrate(III) and NO: Complex formation controlled by outer-sphere electron transfer. Inorg. Chem. 2002;41(21):5417-5425.
http://dx.doi.org/10.1021/ic020288o