Navegar

Colección

Datos Estadísticas

Artículo

El editor solo permite decargar el artículo en su versión post-print desde el repositorio. Por favor, si usted posee dicha versión, enviela a
Consulte el artículo en la página del editor
Consulte la política de Acceso Abierto del editor

Abstract:

The interaction of NO with [Fe(CN)5H2O]3- (generated by aquation of the corresponding ammine complex) to produce [Fe(CN)5NO]3- was studied by UV-vis spectrophotometry. The reaction product is the well characterized nitrosyl complex, described as a low-spin Fe(II) bound to the NO radical. The experiments were performed in the pH range 4-10, at different concentrations of NO, temperatures and pressures. The rate law was first-order in each of the reactants, with the specific complex-formation rate constant, kf = 250 ± 10 M-1 s-1 (25.4 °C, I = 0.1 M, pH 7.0), ΔHf‡ = 70 ± 1 kJ mol-1, ΔSf‡ = +34 ± 4 J K-1 mol-1, and ΔVf‡ = +17.4 ± 0.3 cm3 mol-1. These values support a dissociative mechanism, with rate-controlling dissociation of coordinated water, and subsequent fast coordination of NO. The complex-formation process depends on pH, indicating that the initial product [Fe(CN)5NO]3- is unstable, with a faster decomposition rate at lower pH. The decomposition process is associated with release of cyanide, further reaction of NO with [Fe(CN)4NO]2-, and formation of nitroprusside and other unknown products. The decomposition can be prevented by addition of free cyanide to the solutions, enabling a study of the dissociation process of NO from [Fe(CN)5NO]3-. Cyanide also acts as a scavenger for the [Fe(CN)5]3- intermediate, giving [Fe(CN)6]4- as a final product. From the first-order behavior, the dissociation rate constant was obtained as kd = (1.58 ± 0.06) × 10-5 s-1 at 25.0 °C, I = 0.1 M, and pH 10.2. Activation parameters were found to be ΔHd‡ = 106.4 ± 0.8 kJ mol-1, ΔSd‡ = +20 ± 2 J K-1 mol-1, and ΔVd‡ = +7.1 ± 0.2 cm3 mol-1, which are all in line with a dissociative mechanism. The low value of kd as compared to values for the release of other ligands L from [FeII(CN)5L]n- suggests a moderate to strong σ-π interaction of NO with the iron(II) center. It is concluded that the release of NO from nitroprusside in biological media does not originate from [Fe(CN)5NO]3- produced on reduction of nitroprusside but probably proceeds through the release of cyanide and further reactions of the [Fe(CN)4NO]2- ion.

Registro:

Documento: Artículo
Título:Kinetics and mechanism of the interaction of nitric oxide with pentacyanoferrate(II). Formation and dissociation of [Fe(CN)5NO]3-
Autor:Roncaroli, F.; Olabe, J.A.; Van Eldik, R.
Filiación:Institute for Inorganic Chemistry, University of Erlangen-Nürnberg, Egerlandstrasse 1, 91058 Erlangen, Germany
Dept. of Inorg., Analyt./Phys. Chem., Faculty of Exact, University of Buenos Aires, C1428EHA Buenos Aires, Argentina
Palabras clave:iron derivative; nitric oxide; nitroprusside sodium; pentacyanoferric acid; unclassified drug; article; chemical reaction kinetics; complex formation; concentration response; decomposition; dissociation; molecular interaction; pH; spectrophotometry
Año:2003
Volumen:42
Número:13
Página de inicio:4179
Página de fin:4189
DOI: http://dx.doi.org/10.1021/ic0342189
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
CAS:nitric oxide, 10102-43-9; nitroprusside sodium, 14402-89-2, 15078-28-1
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v42_n13_p4179_Roncaroli

Referencias:

  • Richter-Addo, G.B., Legzdins, P., (1992) Metal Nitrosyls, , Oxford University Press: New York
  • Richter-Addo, G.B., Legzdins, P., Burstyn, J.N., (2002) Chem. Rev., 102, pp. 861-1270
  • Mingos, D.M.P., Sherman, D., (1989) J. Adv. Inorg. Chem., 34, pp. 293-377
  • Feelish, M., Stamler, J.S., (1996) Methods in Nitric Oxide Research, , Wiley: Chichester, England, and references therein
  • (1996) Nitric Oxide, Principles and Actions, , Lancaster, J., Jr., Ed.; Academic Press: New York
  • Butler, A.R., Williams, D.L.H., (1993) Chem. Soc. Rev., 22, pp. 233-241
  • Clarke, M.J., Gaul, J.B., (1993) Struct. Bonding (Berlin), 81, pp. 147-181
  • Butler, A.R., Glidewell, I.C., (1987) Chem. Soc. Rev., 16, pp. 361-380
  • Ford, P.C., Lorkovic, I.M., (2002) Chem. Rev., 102, pp. 993-1018
  • Wolak, M., Van Eldik, R., (2002) Coord. Chem. Rev., 230, pp. 263-282
  • Hoshino, M., Laverman, L., Ford, P.C., (1999) Coord. Chem. Rev., 187, pp. 75-102
  • Baraldo, L.M., Forlano, P., Parise, A.R., Slep, L.D., Olabe, J.A., (2001) Coord. Chem. Rev., 219-221, p. 881
  • Tfouni, E., Krieger, M., McGarvey, B.R., Franco, D.W., (2003) Coord. Chem. Rev., 236, pp. 57-69
  • Callahan, R.W., Meyer, T.J., (1977) Inorg. Chem., 16, pp. 574-581
  • Togano, T., Kuroda, H., Nagao, N., Maekawa, Y., Nishimura, H., Howell, F.S., Mukaida, M., (1992) Inorg. Chim. Acta, 196, pp. 57-63
  • Wanat, A., Schneppensieper, T., Stochel, G., Van Eldik, R., Bill, E., Wieghardt, K., (2002) Inorg. Chem., 41, pp. 4-10
  • Roncaroli, F., Olabe, J.A., Van Eldik, R., (2002) Inorg. Chem., 42, pp. 5417-5425
  • Schneppensieper, T., Finkler, S., Czap, A., Van Eldik, R., Heus, M., Nieuwenhuizen, P., Wreesmann, C., Abma, W., (2001) Eur. J. Inorg. Chem., p. 491
  • Schneppensieper, T., Wanat, A., Stochel, G., Goldstein, S., Meyerstein, D., Van Eldik, R., (2001) Eur. J. Inorg. Chem., p. 2317
  • Schneppensieper, T., Wanat, A., Stochel, G., Van Eldik, R., (2002) Inorg. Chem., 41, p. 2565
  • Westcott, B.L., Enemark, J.L., (1999) Inorganic Electronic Structure and Spectroscopy, Volume II: Applications and Case Studies, 2. , Solomon, E. I., Lever, A. B. P., Eds. Wiley: New York
  • Enemark, J.H., Feltham, R.D., (1974) Coord. Chem. Rev., 13, pp. 339-406
  • Scheidt, W.R., Ellison, M.K., (1999) Acc. Chem. Res., 32, p. 359
  • Macartney, D.H., (1988) Rev. Inorg. Chem., 9, p. 101
  • Kenney, D.J., Flynn, T.P., Gallini, J.B., (1961) J. Inorg. Nucl. Chem., 20, p. 75
  • Toma, E.H., Malin, J.M., (1973) Inorg. Chem., 12, p. 1039
  • Toma, H.E., Malin, J.M., (1973) Inorg. Chem., 12, p. 2080
  • Toma, H.E., Malin, J.M., (1974) Inorg. Chem., 13, pp. 1772-1774
  • Toma, H.E., (1975) Inorg. Chim. Acta, 15, pp. 205-211
  • Szacilowski, K., Stochel, G., Stasicka, Z., Kisch, H., (1997) New J. Chem., 21, pp. 893-902
  • Cheney, R.P., Simic, M.G., Hoffman, M.Z., Taub, I.A., Asmus, K.D., (1977) Inorg. Chem., 16, pp. 2187-2192
  • Van Eldik, R., Palmer, D.A., Schmidt, R., Kelm, H., (1981) Inorg. Chim. Acta, 50, p. 131
  • Van Eldik, R., Gaede, W., Wieland, S., Kraft, J., Spitzer, M., Palmer, D.A., (1993) Rev. Sci. Instrum., 64, p. 1355
  • Binstead, R.A., Zuberbühler, A.D., (1993) Specfit, , Spectrum Software Associates: Chapel Hill, NC
  • Zuberbühler, A.D., (1990) Anal. Chem., 62, p. 2220
  • Spitzer, M., Gärtig, F., Van Eldik, R., (1988) Rev. Sci. Instrum., 59, p. 2092
  • Toma, H.E., Batista, A.A., Gray, H.B., (1982) J. Am. Chem. Soc., 104, pp. 7509-7515
  • Maciejowska, I., Van Eldik, R., Stochel, G., Stasicka, Z., (1997) Inorg. Chem., 36, pp. 5409-5412
  • Fasman, G.D., (1976) Handbook of Biochemistry and Molecular Biology, Physical and Chemical Data, 1. , CRC Press: Cleveland, OH
  • Davies, G., Garafalo, A.R., (1976) Inorg. Chem., 15, pp. 1101-1106
  • Davies, G., Garafalo, A.R., (1980) Inorg. Chem., 19, pp. 3543-3544
  • Malin, J.M., Koch, R.C., (1978) Inorg. Chem., 17, pp. 752-754
  • Zerga, H.O., Olabe, J.A., (1983) Inorg. Chem., 22, pp. 4156-4158
  • Van Voorst, J.D.W., Hemmerich, P., (1966) J. Chem. Phys., 45, pp. 3914-3918
  • Bertolino, J.R., Della Védova, C.O., Sala, O., (1989) Polyhedron, 8, pp. 361-365
  • Nast, R., Schmidt, J., (1969) Angew. Chem., Int. Ed. Engl., 8, p. 383
  • Masek, J., Maslova, E., (1974) Collect. Czech. Chem. Commun., 39, pp. 2141-2160
  • Wanner, M., Scheiring, T., Kaim, W., Slep, L.D., Baraldo, L.M., Olabe, J.A., Zalis, S., Baerends, E., (2001) J. Inorg. Chem., 40, pp. 5704-5707
  • Paliani, G., Poletti, A., Santucci, A., (1971) J. Mol. Struct., 8, pp. 63-74
  • note; Jones, L.H., (1963) Inorg. Chem., 2, pp. 777-780
  • Alexander, J.J., Gray, H.B., (1968) J. Am. Chem. Soc., 90, pp. 4260-4271
  • note; Toma, H.E., Moroi, N.M., Iha, N.Y.M., (1982) An. Acad. Bras. Cienc., 54, pp. 315-323
  • Toma, H.E., Malin, J.M., Giesbrecht, E., (1973) Inorg. Chem., 12, p. 2084
  • Toma, H.E., Martins, J.M., Giesbrecht, E., (1981) J. Chem. Soc., Dalton Trans., pp. 1610-1617
  • Stochel, G., Chatlas, J., Martínez, P., Van Eldik, R., (1992) Inorg. Chem., 31, pp. 5480-5483
  • Finston, M.I., Drickamer, H.G., (1981) J. Phys. Chem., 104, pp. 7509-7515
  • Langford, C.H., Gray, H.B., (1965) Ligand Substitution Processes, , W. A. Benjamin, Inc.: Reading, MA
  • Swaddle, T.W., (1983) Inorg. Chem., 22, pp. 2663-2665
  • note; Legros, J., (1964) J. Chim. Phys. Phys.-Chim. Biol., 61, p. 909
  • Alsheri, S., Burgess, J., (1991) Inorg. Chim. Acta, 181, p. 153
  • Sullivan, T.R., Stranks, D.R., Burgess, J., Haines, R.I., (1977) J. Chem. Soc., Dalton Trans., p. 1460
  • Blandamer, M.J., Burgess, J., Morcom, K.W., Sherry, R., (1983) Transition Met. Chem., 8, p. 354
  • Stochel, G., Van Eldik, R., Hejmo, E., Stasicka, Z., (1988) Inorg. Chem., 27, pp. 2767-2770
  • Bal Reddy, K., Van Eldik, R., (1991) Inorg. Chem., 30, pp. 596-598
  • Bohle, D.S., Hung, C.H., (1995) J. Am. Chem. Soc., 117, p. 9584
  • Lang, D.R., Davis, J.A., Lopes, L.G.F., Ferro, A.A., Vasconcellos, L.C.G., Franco, D.W., Tfouni, E., Clarke, M., (2000) J. Inorg. Chem., 39, pp. 2294-2300
  • Lopes, L.G.F., Wieraszko, A., El-Sherif, Y., Clarke, M.J., (2001) Inorg. Chim. Acta, 312, pp. 15-22
  • note; Laverman, L.E., Hoshino, M., Ford, P.C., (1997) J. Am. Chem. Soc., 119, pp. 12663-12664
  • Laverman, L.E., Wanat, A., Oszajca, J., Stochel, G., Ford, P.C., Van Eldik, R., (2001) J. Am. Chem. Soc., 123, pp. 285-293
  • Schneppensieper, T., Zahl, A., Van Eldik, R., (2001) Angew. Chem., Int. Ed., 40, pp. 1678-1680
  • note

Citas:

---------- APA ----------
Roncaroli, F., Olabe, J.A. & Van Eldik, R. (2003) . Kinetics and mechanism of the interaction of nitric oxide with pentacyanoferrate(II). Formation and dissociation of [Fe(CN)5NO]3-. Inorganic Chemistry, 42(13), 4179-4189.
http://dx.doi.org/10.1021/ic0342189
---------- CHICAGO ----------
Roncaroli, F., Olabe, J.A., Van Eldik, R. "Kinetics and mechanism of the interaction of nitric oxide with pentacyanoferrate(II). Formation and dissociation of [Fe(CN)5NO]3-" . Inorganic Chemistry 42, no. 13 (2003) : 4179-4189.
http://dx.doi.org/10.1021/ic0342189
---------- MLA ----------
Roncaroli, F., Olabe, J.A., Van Eldik, R. "Kinetics and mechanism of the interaction of nitric oxide with pentacyanoferrate(II). Formation and dissociation of [Fe(CN)5NO]3-" . Inorganic Chemistry, vol. 42, no. 13, 2003, pp. 4179-4189.
http://dx.doi.org/10.1021/ic0342189
---------- VANCOUVER ----------
Roncaroli, F., Olabe, J.A., Van Eldik, R. Kinetics and mechanism of the interaction of nitric oxide with pentacyanoferrate(II). Formation and dissociation of [Fe(CN)5NO]3-. Inorg. Chem. 2003;42(13):4179-4189.
http://dx.doi.org/10.1021/ic0342189