Reactions of [Cp(CO)2Fe:CHAr]+ (Ar = p-C6H4OMe) with O:N-Ar'(Ar' = C6H5, p-C6H4NMe2) and PhN:NPh

Abstract

Organometallic products formed from the reaction of an electrophilic iron carbene complex with nitrosoarenes or azobenzene reflect net insertion of the ArN{double bond}X moiety into the Fe{double bond}CHAr bond. Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} and Cp(CO){sub 2}FeN(Ph)-N(Ph){double bond}CHAr{sup +} (Ar = p-C{sub 6}H{sub 4}OMe, Ar{prime} = p-C{sub 6}H{sub 4}NMe{sub 2}) have been isolated and spectroscopically characterized; the crystal structure of Cp(CO){sub 2}Fe-O-N(Ph){double bond}CHAr{sup +} is reported. Exposure of acetone solutions of Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} or Cp(CO){sub 2}FeN(Ph)-N(Ph){double bond}char{sup +} to light yields imine products Ar{prime}N{double bond}CHAr or PhN{double bond}CHAr, respectively. There is no evidence to support the formation of the simple stoichiometric iron-containing products of these reactions, the oxo and nitrene complexes Cp(CO){sub 2}Fe{double bond}O{sup +} and Cp(CO){sub 2}Fe{double bond}NPh{sup +}. Hydrolysis of the nitrone complexes Cp(CO){sub 2}Fe-O-N(Ar{prime}){double bond}CHAr{sup +} in aqueous acetone yields aldehyde products Ar{prime}CHO. 30 refs., 1 fig., 4 tabs.