Synthesis and Characterization of Stable Iron Pentacarbonyl Radical Cation Salts

Abstract

The open-shell iron pentacarbonyl cation [Fe(CO)5].+ was isolated by deelectronation, i.e., the single-electron oxidation of the parent neutral Fe(CO)5 using [phenazineF].+ as the [Al(ORF)4]− and [F-{Al(ORF)3}2]− salt (RF=C(CF3)3; phenazineF=perfluoro-5,10-bis(perfluorophenyl)-5,10-dihydrophenazine). [Fe(CO)5].+[Al(ORF)4]− was fully characterized (scXRD analysis, IR, NMR, EPR, 57Fe spectroscopy, CV and SQUID magnetization study) and, apart from being a compound of fundamental interest, may serve as a precursor for low-valent iron coordination chemistry.