Electrochemical, EPR and Computational Results on [Fe2Cp2(CO)2]-Based Complexes with a Bridging Hydrocarbyl Ligand

摘要: Abstract The dimetallacyclopentenone complexes [Fe2Cp2(CO)(μ−CO){μ−η1:η3−CαH Cβ(R)C( O)}] (R = CH2OH, 1a; R = CMe2OH, 1b; R = Ph, 1c) were prepared by photolytic reaction of [Fe2Cp2(CO)4] with alkyne according to the literature procedure. X-ray and electrochemical characterization 1c are presented. μ-allenyl compound [Fe2Cp2(CO)2(μ−CO){μ−η1:η2α,β−CαH Cβ CMe2][BF4] ([2][BF4]), obtained 1b HBF4, underwent monoelectron reduction give a radical species which was detected EPR at room temperature. signal has been assigned [Fe2Cp2(CO)2(μ−CO){μ−η1:η2α,β–CαH CMe2}], [2]•. molecular structures [2]+ [2]• optimized DFT calculations. unpaired electron in is localized mainly metal centers and, coherently, does not undergo carbon–carbon dimerization, contrast what previously observed for μ-vinyl complex [Fe2Cp2(CO)2(μ−CO){μ−η1:η2–CH CH(Ph)}]•, [3]•. Electron spin density distributions similar one found [Fe2Cp2(CO)2(μ–CO){μ–η1:η2α,β–CαH C(R1)(R2)}]• (R1 = R2 = H, [4]•; R1 = H, R2 = Ph, [5]•; R1 = R2 = Ph, [6]•).