ORGANOMETALLICS: Isolation and structural and electronic characterization of salts of the decamethylferrocene dication

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Abstract

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(ll)/Fe(lll) 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.

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