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Abstract:

The aquapentacyanoferrate(II) ion, [Fe II(CN) 5H 2O] 3-, catalyzes the disproportionation reaction of O-methylhydroxylamine, NH 2OCH 3, with stoichiometry 3NH 2OCH 3 → NH 3 + N 2 + 3CH 3OH. Kinetic and spectroscopic evidence support an initial N coordination of NH 2OCH 3 to [Fe II(CN) 5H 2O] 3- followed by a homolytic scission leading to radicals [Fe II(CN) 5 •NH 2] 3- (a precursor of Fe(III) centers and bound NH 3) and free methoxyl, CH 3O •, thus establishing a radical path leading to N-methoxyamino ( •NHOCH 3) and 1,2-dimethoxyhydrazine, (NHOCH 3) 2. The latter species is moderately stable and proposed to be the precursor of N 2 and most of the generated CH 3OH. Intermediate [Fe III(CN) 5L] 2- complexes (L = NH 3, H 2O) form dinuclear cyano-bridged mixed-valent species, affording a catalytic substitution of the L ligands promoted by [Fe II(CN) 5L] 3-. Free or bound NH 2OCH 3 may act as reductants of [Fe III(CN) 5L] 2-, thus regenerating active sites. At increasing concentrations of NH 2OCH 3 a coordinated diazene species emerges, [Fe II(CN) 5N 2H 2] 3-, which is consumed by the oxidizing CH 3O •, giving N 2 and CH 3OH. Another side reaction forms [Fe II(CN) 5N(O)CH 3] 3-, an intermediate containing the nitrosomethane ligand, which is further oxidized to the nitroprusside ion, [Fe II(CN) 5NO] 2-. The latter is a final oxidation product with a significant conversion of the initial [Fe II(CN) 5H 2O] 3- complex. The side reaction partially blocks the Fe(II)-aqua active site, though complete inhibition is not achieved because the radical path evolves faster than the formation rates of the Fe II-NO + bonds. © 2011 American Chemical Society.

Registro:

Documento: Artículo
Título:Disproportionation of O-methylhydroxylamine catalyzed by aquapentacyanoferrate(II)
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, Ciudad Universitaria, Universidad de Buenos Aires, Pabellón 2, C1428EHA, Buenos Aires, Argentina
Palabras clave:aquapentacyanoferrate; ferrocyanide; free radical; hydroxylamine; methoxyamine; article; catalysis; chemistry; kinetics; spectroscopy; Catalysis; Ferrocyanides; Free Radicals; Hydroxylamines; Kinetics; Spectrum Analysis
Año:2011
Volumen:50
Número:18
Página de inicio:8817
Página de fin:8825
DOI: http://dx.doi.org/10.1021/ic2007155
Título revista:Inorganic Chemistry
Título revista abreviado:Inorg. Chem.
ISSN:00201669
CODEN:INOCA
CAS:ferrocyanide, 13408-63-4, 13601-19-9; hydroxylamine, 7803-49-8; methoxyamine, 67-62-9; Ferrocyanides; Free Radicals; Hydroxylamines; aquapentacyanoferrate, 14100-31-3; methoxyamine, 67-62-9
Registro:https://bibliotecadigital.exactas.uba.ar/collection/paper/document/paper_00201669_v50_n18_p8817_Gutierrez

Referencias:

  • Wieghardt, K., (1984) Adv. Inorg. Bioinorg. Mech., 3, p. 213
  • Rappoport, Z., Liebman, J.F., (2008) The Chemistry of Hydroxylamines, Oximes and Hydroxamic Acids, , Wiley: New York
  • Gross, P., (1985) Crit. Rev. Toxicol., 14, p. 87
  • Stedman, G.Adv., (1979) Inorg. Chem. Radiochem., 22, p. 113
  • Hung, M.L., McKee, M.L., Stanbury, D.M., (1994) Inorg. Chem., 33, p. 5108
  • Makarycheva-Mikhailova, A.V., Stanbury, D.M., McKee, M.L., (2007) J. Phys. Chem. B, 111, p. 6942
  • Liu, R.M., McDonald, M.R., Margerum, D.W., (1995) Inorg. Chem., 34, p. 6093
  • Johnson, M.D., Hornstein, B.J., (2003) Inorg. Chem., 42, p. 6923
  • Lockamy, V.L., Shields, H., Kim-Shapiro, D.B., King, S.B., (2004) Biochim. Biophys. Acta, 1674, p. 260
  • Benjamin, E., Hijjy, Y., (2008) Molecules, 13, p. 157
  • Albertin, G., Antoniutti, S., Bravo, J., Castro, J., García-Fontan, S., Martin, M.C., Noe, M., (2006) Eur. J. Inorg. Chem., p. 3451
  • Wu, A., Mader, E.A., Datta, A., Hrovat, D.A., Borden, W.T., Mayer, J.M., (2009) J. Am. Chem. Soc., 131, p. 11985
  • Davies, G., Kustin, K., (1969) Inorg. Chem., 8, p. 484
  • Honig, D.S., Kustin, K., Martin, J.F., (1972) Inorg. Chem., 11, p. 1895
  • Swaroop, R., Gupta, Y.K., (1974) J. Inorg. Nucl. Chem., 36, p. 169
  • Alluisetti, G.B., Almaraz, A.E., Amorebieta, V.T., Doctorovich, F., Olabe, J.A., (2004) J. Am. Chem. Soc., 126, p. 13432
  • Gutiérrez, M.M., Alluisetti, G.B., Gaviglio, C., Doctorovich, F., Olabe, J.A., Amorebieta, V.T., (2009) Dalton Trans., p. 1187
  • Bari, S.E., Amorebieta, V.T., Gutiérrez, M.M., Olabe, J.A., Doctorovich, F., (2010) J. Inorg. Biochem., 104, p. 30
  • Choi, I., Liu, Y., Wei, Z., Ryan, M.D., (1997) Inorg. Chem., 36, p. 3113
  • Bazylinski, D.A., Arkowitz, R.A., Hollocher, T.C., (1987) Arch. Biochem. Biophys., 259, p. 520
  • Gutiérrez, M.M., Alluisetti, G.B., Olabe, J.A., Amorebieta, V.T., (2008) Dalton Trans., p. 5025
  • Olabe, J.A., Estiú, G.L., (2003) Inorg. Chem., 42, p. 4873
  • Wolfe, S.K., Andrade, C., Swinehart, J.H., (1974) Inorg. Chem., 13, p. 2567
  • Gillard, R.D., McCleverty, J.A., (1987) Comprehensive Coordination Chemistry, , Elsevier Ltd. New York
  • McCleverty, J.A., Meyer, T.J., (2004) Comprehensive Coordination Chemistry II, , Elsevier Ltd. New York
  • Lunak, S., Veprek-Siska, J., (1974) Collect. Czech. Chem. Commun., 39, p. 41
  • Lunak, S., Veprek-Siska, J., (1974) Collect. Czech. Chem. Commun., 39, p. 391
  • Bonner, F.T., Akhtar, M.J., (1981) Inorg. Chem., 20, p. 3155
  • Bridgart, G.J., Waters, W.A., Wilson, I.R., (1973) J. Chem. Soc., Dalton Trans., p. 1582
  • Toma, H.E., Malin, J.M., (1973) Inorg. Chem., 12 (1039), p. 2080
  • Toma, H.E., Malin, J.M., (1975) J. Am. Chem. Soc., 97, p. 288
  • Olabe, J.A., (2008) Dalton Trans., p. 3633
  • Baraldo, L.M., Forlano, P., Parise, A.R., Slep, L.D., Olabe, J.A., (2001) Coord. Chem. Rev., 219-221, p. 881
  • MacArtney, D.H., (1988) Rev. Inorg. Chem., 6, p. 101
  • Olabe, J.A., (2004) Adv. Inorg. Chem., 55, p. 61
  • Liao, Y., Syn, M., Xu, Y., (2002) J. Liq. Chromogr. Related Technol., 28, p. 2433. , references cited therein
  • Wang, E., Struble, E., Liu, P., Cheung, A.P., (2002) J. Pharm. Biomed. Anal., 30, p. 415. , references cited therein
  • Kenney, D.J., Flynn, T.P., Gallini, J.B., (1961) J. Inorg. Nucl. Chem., 20, p. 75
  • Chacón Villalba, M.E., Varetti, E.L., Aymonino, P.J., (1997) Vib. Spectrosc., 14, p. 275
  • Bissot, T.C., Parry, R.W., Campbell, D.H., (1957) J. Am. Chem. Soc., 79, p. 796
  • Olabe, J.A., Zerga, H.O., (1983) Inorg. Chem., 22, p. 4156
  • Toma, H.E., (1975) Inorg. Chim. Acta, 15, p. 205
  • Espenson, J.H., Wolenuk Jr., S.G., (1972) Inorg. Chem., 11, p. 2034
  • Emschwiller, G., (1967) C. R. Acad. Sci. Paris, 265, p. 281
  • Emschwiller, G., Jorgensen, C.K., (1970) Chem. Phys. Lett., 5, p. 561
  • Souto, M.F., Cukiernik, F.D., Forlano, P., Olabe, J.A., (2001) J. Coord. Chem., 54, p. 343
  • Gale, R., McCaffery, A.J., (1973) J. Chem. Soc., Dalton Trans., p. 1344
  • Brauer, G., (1965) Handbook of Preparative Inorganic Chemistry, , 2 nd ed. Academic Press: New York
  • MacArtney, D.H., Mc Auley, A., (1981) Can. J. Chem., 59, p. 132
  • (1994) NIOSH Manual of Analytical Methods, Method N° 3500, , 4th ed
  • Koroleff, F., (1976) Methods of Seawater Analysis, , Grasshoft, K. Verlag Chemie: New York
  • Adachi, S., (1965) Anal. Chem., 37, p. 896
  • Szacilowski, K., Stochel, G., Stasicka, Z., Kisch, H., (1997) New J. Chem., 21, p. 893
  • Roncaroli, F., Olabe, J.A., Van Eldik, R., (2002) Inorg. Chem., 41, p. 5417
  • Testa, J.J., Grela, M.A., Litter, M.I., (2004) Environ. Sci. Technol., 38, p. 1589
  • Janzen, E.G., (1971) Acc. Chem. Res., 4, p. 31
  • Rehorek, D., (1991) Chem. Soc. Rev., 20, p. 341
  • http://tools.niesh.nih.gov/stdb/index.cfm, Niehs spin trap database; Gear, C.W., (1971) Comun. ACM, 14, p. 176
  • Toma, H.E., Batista, A.A., Gray, H.B., (1982) J. Am. Chem. Soc., 104, p. 7509
  • James, A.D., Murray, R.S., Higginson, W.C.E., (1974) J. Chem. Soc., Dalton Trans., p. 1273
  • Schwane, J.D., Ashby, M.T., (2002) J. Am. Chem. Soc., 124, p. 6822
  • Guo, Q., Qian, S.Y., Mason, R.P., (2003) J. Am. Soc. Mass Spectrom., 14, p. 862
  • Dikalov, S.I., Mason, R.P., (1999) Free Radical Biol. Med., 27, p. 864
  • Makino, K., Hagi, A., Ide, H., Murakami, A., (1992) Can. J. Chem., 70, p. 2818
  • Britigan, B.E., Coffman, T.J., Buettner, G.R., (1990) J. Biol. Chem., 265, p. 2650
  • Stanbury, D.M., (2010) Physical Inorganic Chemistry. Reactions, Processes and Applications, p. 409. , Bakac, A. Wiley: New York, Chapter 9
  • Simic, M., Hayon, E., (1971) J. Am. Chem. Soc., 93, p. 5982
  • Neta, P., Maruthamuthu, P., Carton, P.M., Fessenden, R.W., (1978) J. Phys. Chem., 82, p. 1875
  • Bakac, A., Simunic, J.L., Espenson, J.H., (1990) Inorg. Chem., 29, p. 1090
  • Stasiw, R., Wilkins, R.G., (1969) Inorg. Chem., 8, p. 156
  • Kochi, J.K., (1973) Free Radicals, 2. , Wiley: New York
  • Kaba, R.A., Ingold, K.U., (1976) J. Am. Chem. Soc., 98, p. 7375
  • Malatesta, B., Ingold, K.U., (1974) J. Am. Chem. Soc., 96, p. 3949
  • Carey, F.A., Hayes, L.J., (1973) J. Org. Chem., 38, p. 3107
  • Lehnert, N., Wiesler, B.E., Tuczek, F., Hennige, A., Sellmann, D., (1997) J. Am. Chem. Soc., 119, p. 8869
  • Cheney, R.P., Simic, M.G., Hoffman, M.Z., Taub, I.A., Asmus, K.D., (1977) Inorg. Chem., 16, p. 2187
  • Socrates, G., (1998) Infrared Characteristic Group Frequencies. Tables and Charts, , 2 nd ed. Wiley: New York
  • Cheney, R.P., Pell, S.D., Hoffman, M.Z., (1979) J. Inorg. Nucl. Chem., 41, p. 489

Citas:

---------- APA ----------
Gutiérrez, M.M., Olabe, J.A. & Amorebieta, V.T. (2011) . Disproportionation of O-methylhydroxylamine catalyzed by aquapentacyanoferrate(II). Inorganic Chemistry, 50(18), 8817-8825.
http://dx.doi.org/10.1021/ic2007155
---------- CHICAGO ----------
Gutiérrez, M.M., Olabe, J.A., Amorebieta, V.T. "Disproportionation of O-methylhydroxylamine catalyzed by aquapentacyanoferrate(II)" . Inorganic Chemistry 50, no. 18 (2011) : 8817-8825.
http://dx.doi.org/10.1021/ic2007155
---------- MLA ----------
Gutiérrez, M.M., Olabe, J.A., Amorebieta, V.T. "Disproportionation of O-methylhydroxylamine catalyzed by aquapentacyanoferrate(II)" . Inorganic Chemistry, vol. 50, no. 18, 2011, pp. 8817-8825.
http://dx.doi.org/10.1021/ic2007155
---------- VANCOUVER ----------
Gutiérrez, M.M., Olabe, J.A., Amorebieta, V.T. Disproportionation of O-methylhydroxylamine catalyzed by aquapentacyanoferrate(II). Inorg. Chem. 2011;50(18):8817-8825.
http://dx.doi.org/10.1021/ic2007155