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Abstract:

The reaction kinetics of a set of ruthenium nitrosyl complexes, {(X) 5MNO}n, containing different coligands X (polypyridines, NH3, EDTA, pz, and py) with cysteine (excess conditions), were studied by UV-vis spectrophotometry, using stopped-flow techniques, at an appropriate pH, in the range 3-10, and T = 25°C. The selection of coligands afforded a redox-potential range from -0.3 to +0.5 V (vs Ag/AgCl) for the NO+/NO bound couples. Two intermediates were detected. The first one, I1, appears in the range 410-470 nm for the different complexes and is proposed to be a 1:1 adduct, with the S atom of the cysteinate nucleophile bound to the N atom of nitrosyl. The adduct formation step of I1 is an equilibrium, and the kinetic rate constants for the formation and dissociation of the corresponding adducts were determined by studying the cysteine-concentration dependence of the formation rates. The second intermediate, I2, was detected through the decay of I1, with a maximum absorbance at ca. 380 nm. From similar kinetic results and analyses, we propose that a second cysteinate adds to I1 to form I2. By plotting ln k1(RS-) and ln k2(Rs-) for the first and second adduct formation steps, respectively, against the redox potentials of the NO+/NO couples, linear free energy plots are obtained, as previously observed with OH- as a nucleophile. The addition rates for both processes increase with the nitrosyl redox potentials, and this reflects a more positive charge at the electrophilic N atom. In a third step, the I2 adducts decay to form the corresponding Ru-aqua complexes, with the release of N2O and formation of cystine, implying a two-electron process for the overall nitrosyl reduction. This is in contrast with the behavior of nitroprusside ([Fe(CN)5NO]2-; NP), which always yields the one-electron reduction product, [Fe(CN) 5NO]3-, either under substoichiometric or in excess-cysteine conditions. © 2005 American Chemical Society.

Registro:

Documento: Artículo
Título:The reactions of nitrosyl complexes with cysteine
Autor:Roncaroli, F.; Olabe, J.A.
Filiación:Departamento de Quimica Inorganica, Analitica Y Quimica Fisica - INQUIMAE, Facultad de Ciencias Exactas Y Naturales, Ciudad Universitaria, Buenos Aires C1428EHA, Argentina
Palabras clave:cysteine; ligand; nitrogen oxide; nitroprusside sodium; article; chemistry; electrochemistry; electrode; kinetics; oxidation reduction reaction; pH; thermodynamics; ultraviolet spectrophotometry; Cysteine; Electrochemistry; Electrodes; Hydrogen-Ion Concentration; Kinetics; Ligands; Nitrogen Oxides; Nitroprusside; Oxidation-Reduction; Spectrophotometry, Ultraviolet; Thermodynamics
Año:2005
Volumen:44
Número:13
Página de inicio:4719
Página de fin:4727
DOI: http://dx.doi.org/10.1021/ic048156d
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
CAS:cysteine, 4371-52-2, 52-89-1, 52-90-4; nitrogen oxide, 11104-93-1; nitroprusside sodium, 14402-89-2, 15078-28-1; Cysteine, 52-90-4; Ligands; Nitrogen Oxides; Nitroprusside, 15078-28-1
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v44_n13_p4719_Roncaroli

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Citas:

---------- APA ----------
Roncaroli, F. & Olabe, J.A. (2005) . The reactions of nitrosyl complexes with cysteine. Inorganic Chemistry, 44(13), 4719-4727.
http://dx.doi.org/10.1021/ic048156d
---------- CHICAGO ----------
Roncaroli, F., Olabe, J.A. "The reactions of nitrosyl complexes with cysteine" . Inorganic Chemistry 44, no. 13 (2005) : 4719-4727.
http://dx.doi.org/10.1021/ic048156d
---------- MLA ----------
Roncaroli, F., Olabe, J.A. "The reactions of nitrosyl complexes with cysteine" . Inorganic Chemistry, vol. 44, no. 13, 2005, pp. 4719-4727.
http://dx.doi.org/10.1021/ic048156d
---------- VANCOUVER ----------
Roncaroli, F., Olabe, J.A. The reactions of nitrosyl complexes with cysteine. Inorg. Chem. 2005;44(13):4719-4727.
http://dx.doi.org/10.1021/ic048156d