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Abstract:

Hydroxyurea (HU, NH2CONHOH), reacts with several oxidizing agents (O2, H2O2, IO4-, Fe(III) complexes) in aqueous solutions containing either of the pentacyano(aqua)ferrate(II,III) ions, [FeII,III(CN)5H 2O]3,2-. In the initial 1-electron step, HU reacts with [FeIII(CN)5H2O]2- through an outer-sphere process, leading to [FeII(CN)5H 2O]3- and the EPR active nitroxide radical, NH 2C(O)NHȮ. This is further oxidized to C-nitrosoformamide, NH2C(O)NO, in a similar 1-electron step. The latter compound binds to [FeII(CN)5H2O] 3- giving the [FeII(CN)5(NOC(O)NH 2)]3- ion (I3-). I3- has been isolated as a solid, Na3[FeII(CN)5(NOC(O) NH2)]·2H2O, (I), and was identified by chemical analysis, IR and UV-Vis spectroscopies (λmax = 465 nm, = 4.0 ± 0.3 × 103 M-1 cm-1). I and I3- are very stable species in anaerobic media, as solids and in aqueous solutions with a pH close to 7. I3- decomposes in alkaline media through hydrolysis, giving CO2, NH3 and, presumably, the nitroxyl complex [FeII(CN)5NO]4-. The latter ion appears as a source of N2O, detected by mass spectrometry, and affords, in oxygenated media, two subsequent 1-electron processes, without the rupture of the NO bond, giving the radical intermediate [Fe II(CN)5NO•]3- (which was identified by UV-Vis and EPR), and finally the nitroprusside ion, [Fe(CN) 5NO]2-. At pHs > 10, the latter ion may convert to [FeII(CN)5NO2]4-, and leads to [FeII(CN)5H2O]3- through the release of nitrite. Thus, the aqua-ion might afford a new 4-electron oxidation process if HU and the external oxidant were in excess. © 2011 Elsevier B.V. All rights reserved.

Registro:

Documento: Artículo
Título:Catalytic oxidation of hydroxyurea to bound NO+/ NO2 - Mediated by pentacyano(L)ferrates. Characterization of the nitroxide radical, bound C-nitrosoformamide and NO• as reaction intermediates
Autor:Montenegro, A.C.; Dabrowski, S.G.; Gutiérrez, M.M.; Amorebieta, V.T.; Bari, S.E.; Olabe, J.A.
Filiación:Department of Inorganic, Analytical and Physical Chemistry, INQUIMAE, Pabellón 2, C1428EHA, Buenos Aires, Argentina
Department of Chemistry, Facultad de Ciencias Exactas y Naturales, Universidad Nacional de Mar Del Plata, Funes y Roca, Mar del Plata B7602AYL, Argentina
Palabras clave:C-nitrosoformamide; Hydroxyurea; Nitroxide; Nitroxyl; Pentacyano(L)ferrates
Año:2011
Volumen:374
Número:1
Página de inicio:447
Página de fin:452
DOI: http://dx.doi.org/10.1016/j.ica.2011.02.051
Título revista:Inorganica Chimica Acta
Título revista abreviado:Inorg. Chim. Acta
ISSN:00201693
CODEN:ICHAA
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201693_v374_n1_p447_Montenegro

Referencias:

  • Wang, P.G., Xian, M., Tang, X., Wu, X., Wen, Z., Cai, T., Janczuk, A.J., (2002) Chem. Rev., 102, p. 1091
  • King, S.B., (2005) Curr. Top. Med. Chem., 5, p. 665
  • Kovacic, P., (2011) Med. Hypotheses, 76, p. 24
  • Huang, J.M., Sommers, E.M., Kim-Shapiro, D.B., King, S.B., (2002) J. Am. Chem. Soc., 124, p. 3473
  • Huang, J.M., Kim-Shapiro, D.B., King, S.B., (2004) J. Med. Chem., 47, p. 3495
  • Gabricevic, M., Besic, E., Birus, M., Zahl, A., Van Eldik, R., (2006) J. Inorg. Biochem., 100, p. 1606
  • Chatterjee, D., Nayak, K.A., Ember, E., Van Eldik, R., (2010) Dalton Trans., 39, p. 1695
  • Olabe, J.A., (2008) Dalton Trans., 28, p. 3633
  • Toma, H.E., (1975) Inorg. Chim. Acta, 15, p. 205
  • Kenney, D.J., Flynn, T.P., Gallini, J.B., (1961) J. Inorg. Nucl. Chem., 20, p. 75
  • Schwane, J.D., Ashby, M.T., (2002) J. Am. Chem. Soc., 124, p. 6822
  • Olabe, J.A., (2004) Adv. Inorg. Chem., 55, p. 61
  • Brauer, G., (1965) Handbook of Preparative Inorganic Chemistry, , second ed. Academic Press New York
  • Espenson, J.H., Wolenuk, S.G., (1972) Inorg. Chem., 11, p. 2034
  • MacArtney, D.H., Mc Auley, A., (1981) Can. J. Chem., 59, p. 132
  • Toma, H.E., Malin, J.M., (1973) Inorg. Chem., 12, p. 1039
  • Koroleff, F., (1976) Methods of Seawater Analysis, p. 126. , K. Grasshoft, Verlag Chemie New York
  • Szacilowski, K., Stochel, G., Stasicka, Z., Kisch, H., (1977) New J. Chem., 21, p. 893
  • Roncaroli, F., Olabe, J.A., Van Eldik, R., (2002) Inorg. Chem., 41, p. 5417
  • Cheney, R.P., Simic, M.G., Hoffman, M.Z., Taub, I.A., Asmus, D.K., (1977) Inorg. Chem., 16, p. 2187
  • NIESH Spin Trap Data Base, , http://tools.niesh.nih.gov/stdb/index.cfm
  • Gutiérrez, M.M., Amorebieta, V.T., Estiú, G.L., Olabe, J.A., (2002) J. Am. Chem. Soc., 124, p. 10307
  • Alluisetti, G., Almaraz, A.E., Amorebieta, V.T., Doctorovich, F., Olabe, J.A., (2004) J. Am. Chem. Soc., 126, p. 13432
  • Cohen, A.D., Zeng, B.B., King, S.B., Toscano, J.P., (2003) J. Am. Chem. Soc., 125, p. 1444
  • Montenegro, A.C., Amorebieta, V.T., Slep, L.D., Martín, D.F., Roncaroli, F., Murgida, D.H., Bari, S.E., Olabe, J.A., (2009) Angew. Chem., Int. Ed., 48, p. 4213
  • Gutiérrez, M.M., Alluisetti, G.B., Olabe, J.A., Amorebieta, V.T., (2009) Dalton Trans., p. 1187
  • Lassmann, G., Liermann, B., (1989) Free Rad. Biol. Med., 6, p. 241
  • Toma, H.E., Malin, J.M., (1973) Inorg. Chem., 12, p. 2080
  • Roncaroli, F., Olabe, J.A., Van Eldik, R., (2003) Inorg. Chem., 42, p. 4179
  • Bradic, Z., Pribanic, M., Asperger, S., (1975) J. Chem. Soc., Dalton Trans., p. 353
  • Atkinson, R.N., Storey, B.M., King, S.B., (1996) Tetrahedron Lett., 37, p. 9287
  • Olabe, J.A., Zerga, H.O., (1983) Inorg. Chem., 22, p. 4156
  • Videla, M., Roncaroli, F., Slep, L.D., Olabe, J.A., (2007) J. Am. Chem. Soc., 129, p. 278
  • Van Voorst, J.D.W., Hemmerich, P., (1966) J. Chem. Phys., 45, p. 3914
  • Wanner, M., Scheiring, T., Kaim, W., Slep, L.D., Baraldo, L.M., Olabe, J.A., Zalis, S., Baerends, E.J., (2001) Inorg. Chem., 40, p. 5704
  • Szacilowski, K., Wanat, A., Barbieri, A., Wasielewska, E., Witko, M., Stochel, G., Stasicka, Z., (2002) New J. Chem., 26, p. 1495
  • Arulsamy, N., Scott Bohle, D., Imonigie, J.A., Moore, R.C., (2007) Inorg. Chem., 26, p. 4737
  • Poskrebyshev, G.A., Shafirovich, V., Lymar, S.V., (2008) J. Phys. Chem., 112, p. 8295
  • Reisz, J.A., Bechtold, E., King, S.B., (2010) Dalton Trans., 39, p. 5203
  • Adak, S., Wang, W., Stuehr, D.J., (2000) J. Biol. Chem., 275, p. 33554
  • Miranda, K.M., (2005) Coord. Chem. Rev., 249, p. 433

Citas:

---------- APA ----------
Montenegro, A.C., Dabrowski, S.G., Gutiérrez, M.M., Amorebieta, V.T., Bari, S.E. & Olabe, J.A. (2011) . Catalytic oxidation of hydroxyurea to bound NO+/ NO2 - Mediated by pentacyano(L)ferrates. Characterization of the nitroxide radical, bound C-nitrosoformamide and NO• as reaction intermediates. Inorganica Chimica Acta, 374(1), 447-452.
http://dx.doi.org/10.1016/j.ica.2011.02.051
---------- CHICAGO ----------
Montenegro, A.C., Dabrowski, S.G., Gutiérrez, M.M., Amorebieta, V.T., Bari, S.E., Olabe, J.A. "Catalytic oxidation of hydroxyurea to bound NO+/ NO2 - Mediated by pentacyano(L)ferrates. Characterization of the nitroxide radical, bound C-nitrosoformamide and NO• as reaction intermediates" . Inorganica Chimica Acta 374, no. 1 (2011) : 447-452.
http://dx.doi.org/10.1016/j.ica.2011.02.051
---------- MLA ----------
Montenegro, A.C., Dabrowski, S.G., Gutiérrez, M.M., Amorebieta, V.T., Bari, S.E., Olabe, J.A. "Catalytic oxidation of hydroxyurea to bound NO+/ NO2 - Mediated by pentacyano(L)ferrates. Characterization of the nitroxide radical, bound C-nitrosoformamide and NO• as reaction intermediates" . Inorganica Chimica Acta, vol. 374, no. 1, 2011, pp. 447-452.
http://dx.doi.org/10.1016/j.ica.2011.02.051
---------- VANCOUVER ----------
Montenegro, A.C., Dabrowski, S.G., Gutiérrez, M.M., Amorebieta, V.T., Bari, S.E., Olabe, J.A. Catalytic oxidation of hydroxyurea to bound NO+/ NO2 - Mediated by pentacyano(L)ferrates. Characterization of the nitroxide radical, bound C-nitrosoformamide and NO• as reaction intermediates. Inorg. Chim. Acta. 2011;374(1):447-452.
http://dx.doi.org/10.1016/j.ica.2011.02.051