The substituted hydroxylamines, CH(3)N(H)OH (N-methylhydroxylamine) and (CH(3))(2)NOH (N,N-dimethylhydroxylamine), disproportionate catalytically to the corresponding alkylamines and oxidation products, only in the presence of [Fe(CN)(5)H(2)O](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 (RNCH(3)) and nitroxide (RN(CH(3))O) radicals (R = H, CH(3)). With CH(3)N(H)OH, bound nitrosomethane, CH(3)NO, 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.