Producción CyT
Artículo
Autoría
Gutiérrez, María M.
;
Alluisetti, Graciela Beatriz
;
Olabe Iparraguirre, Jose Antonio
;
Amorebieta, Valentín Tomás
Fecha
2009
Editorial y Lugar de Edición
Royal Society of Chemistry
Revista
DALTON TRANSACTIONS,
vol. 7
(pp. 1187-1194)
Royal Society of Chemistry
Resumen
Información suministrada por el agente en
SIGEVA
The substituted hydroxylamines, CH3N(H)OH (N-methylhydroxylamine) and (CH3)2NOH (N,N-dimethylhydroxylamine), disproportionate catalytically to the corresponding alkylamines and oxidation products, only in the presence of [Fe(CN)5H2O]3?. Substitution kinetic measurements suggest an initial coordination step to Fe(ii). Two parallel N- and O-coordination modes are considered with the subsequent formation of Fe(iii), free aminyl (RNCH3) and nitroxide (RN(CH3)O) radicals (R = H, CH3). With CH3N(H)OH...
The substituted hydroxylamines, CH3N(H)OH (N-methylhydroxylamine) and (CH3)2NOH (N,N-dimethylhydroxylamine), disproportionate catalytically to the corresponding alkylamines and oxidation products, only in the presence of [Fe(CN)5H2O]3?. Substitution kinetic measurements suggest an initial coordination step to Fe(ii). Two parallel N- and O-coordination modes are considered with the subsequent formation of Fe(iii), free aminyl (RNCH3) and nitroxide (RN(CH3)O) radicals (R = H, CH3). With CH3N(H)OH, bound nitrosomethane, CH3NO, has been characterized by UV-visible and IR spectroscopies. The mechanism is discussed on the basis of common and differential features with respect to the disproportionation of hydroxylamine catalyzed by the same Fe-fragment.
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Palabras Clave
CH3NCH3NOHYDROXYLAMINES
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