Electrochemical, EPR and computational results on [Fe2Cp2(CO)2]-based complexes with a bridging hydrocarbyl ligand |
| |
Authors: | Adriano Boni Tiziana Funaioli Guido Pampaloni Stefano Zacchini |
| |
Affiliation: | a University of Pisa, Dipartimento di Chimica e Chimica Industriale, Via Risorgimento 35, 56126 Pisa, Italy b Scuola Normale Superiore, Piazza dei Cavalieri, I-56126 Pisa, Italy c ICCOM-CNR UOS, Area della Ricerca, Via Moruzzi 1, 56124 Pisa (I), Italy d University of Bologna, Dipartimento di Chimica Fisica e Inorganica, Viale Risorgimento 4, 40136 Bologna, Italy |
| |
Abstract: | The dimetallacyclopentenone complexes [Fe2Cp2(CO)(μ−CO){μ−η1:η3−CαHCβ(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. The X-ray and the electrochemical characterization of 1c are presented. The μ-allenyl compound [Fe2Cp2(CO)2(μ−CO){μ−η1:η2α,β−CαHCβCMe2][BF4] ([2][BF4]), obtained by reaction of 1b with HBF4, underwent monoelectron reduction to give a radical species which was detected by EPR at room temperature. The EPR signal has been assigned to [Fe2Cp2(CO)2(μ−CO){μ−η1:η2α,β-CαHCβCMe2}], [2]•. The molecular structures of [2]+ and [2]• were optimized by DFT calculations. The unpaired electron in [2]• is localized mainly at the metal centers and, coherently, [2]• does not undergo carbon-carbon dimerization, by contrast with what previously observed for the μ-vinyl radical complex [Fe2Cp2(CO)2(μ−CO){μ−η1:η2-CHCH(Ph)}]•, [3]•. Electron spin density distributions similar to the one of [2]• were found for the μ-allenyl radical complexes [Fe2Cp2(CO)2(μ-CO){μ-η1:η2α,β-CαHCβC(R1)(R2)}]• (R1 = R2 = H, [4]•; R1 = H, R2 = Ph, [5]•; R1 = R2 = Ph, [6]•). |
| |
Keywords: | Diiron complexes Dimetallacyclopentenone complexes Allenyl ligand Vinyl ligand Electrochemistry DFT calculations |
本文献已被 ScienceDirect 等数据库收录! |
|