Isolation and structural and electronic characterization of salts of the decamethylferrocene dication
M. Malischewski, M. Adelhardt, J. Sutter, K. Meyer, K. Seppelt – 2016
Ferrocene and its decamethyl derivative [Cp*2Fe] are the most common standards for nonaqueous electrochemical investigations because of their well-defined and only mildly solvent-dependent reversible Fe(II)/Fe(III) redox couple. Higher oxidation states have only rarely been studied. We report the isolation and crystallographic and spectroscopic characterization of surprisingly stable Fe(IV) salts of the [Cp*2Fe]2+ dication, produced by oxidation of [Cp*2Fe] with AsF5, SbF5, or ReF6 in neat sulfur dioxide as well as [XeF](Sb2F11) in neat hydrogen fluoride. The Sb2F11– salt exhibits a metallocene with the expected mutually parallel arrangements of the Cp* rings, whereas the As2F11–, AsF6–, SbF6–, and ReF6– salts manifest tilt angles ranging from 4° to 17°. Both 57Fe Mössbauer spectroscopy and superconducting quantum interference device magnetization studies reveal identical d-orbital splitting with an S = 1, 3E ground state based on the 3d electronic configuration e2g3a1g1 of all [Cp*2Fe]2+ salts.