Catalytic Disproportionation of N-alkylhydroxylamines bound to pentacyanoferrates

M.M. GUTIÉREZ, G.B. ALLUISETTI, J.A. OLABE, V.T. AMOREBIETA

JOURNAL OF THE CHEMICAL SOCIETY, DALTON TRANSACTIONS

RSC

Año: 2009 p. 1187 - 1194

0300-9246

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-vis and IR spectroscopies. The mechanism is discussed on the basis of common and differential features with respect to the disproportination of hydroxylamine catalyzed by the same Fe-fragment.