The reactions of nitrosoarenes with the (cyclohexadienyl)Fe(CO)3 cation have been investigated by using electron spin resonance spectroscopy. The radicals produced are nitroxides of the type (OC)3Fe(C6H7)(Ar)N—O• but, in some cases, disproportionation and loss of the metal carbonyl fragment leads to the corresponding C6H5(Ar)N—O• radical. With bulky nitrosoarenes, such as C6Me5NO, isomers are observed in which the aryl ring rotation is slow on the ESR time scale. The analogous reactions with the cyclohexadienyl cation derived from the B ring of (ergosteryl acetate)Fe(CO)3 lead to initial attack not at one of the termini of the delocalized system but rather at the central carbon, i.e., at C-7. Subsequent hydrogen migration leads to the (5,7-diene)Fe(CO)3 complex bearing the arylnitroxide at the 7-position. The mechanisms of these reactions are discussed. Keywords: nitrosoarenes, iron cations, ESR.