INVESTIGADORES
GAVIGLIO Carina Del Valle
artículos
Título:
Catalytic disproportionation of N-alkylhydroxilamines bound to pentacyanoferrates
Autor/es:
MARIA M. GUTIERREZ; GRACIELA ALLUISETTI; CARINA GAVIGLIO; FABIO DOCTOROVICH; JOSE A. OLABE; VALENTIN AMOREBIETA
Revista:
JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS
Editorial:
The Royal Society of Chemistry
Referencias:
Año: 2009 p. 1187 - 1194
ISSN:
0300-9246
Resumen:
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.