A decacationic ferrocene-based metallostar

Abstract

Decacationic metallostars have been prepared by the reaction of permercurated ferrocene FeC₁₀(HgO₂CCF₃)₁₀ with superacidic (C₅F₅NH)(SbF₆) (pK_a = −11 estimated in H₂O) in multigram scale. In the resulting compound, [FeC₁₀Hg₁₀(NC₅F₅)_n][SbF₆]₁₀, the labile pentafluoropyridine ligands are readily displaced by acetonitrile (MeCN) or tetrahydrothiophene (THT). In the X-ray structure of [FeC₁₀Hg₁₀(THT)₁₀][SbF₆]₁₀·24 MeCN no cation–anion contacts between mercury and fluorine were observed. Moreover, cyclic voltammetry measurements of [FeC₁₀(Hg(MeCN))₁₀]¹⁰⁺ and [FeC₁₀(Hg(THT))₁₀]¹⁰⁺ revealed a (quasi)reversible one-electron oxidation of Fe(II) to Fe(III). From the reaction of [FeC₁₀(Hg(MeCN))₁₀]¹⁰⁺ with MoF₆ as oxidant the ferrocenium cation [FeC₁₀(Hg(MeCN))₁₀]¹¹⁺ was obtained and characterized via single crystal XRD. These electrophilic metallostars are promising potential building blocks for the synthesis of dendritic architectures containing a robust, tenfold functionalized ferrocene core.