Bis-Arene Complexes [Re(η-arene)] as Highly Stable Bioorganometallic Scaffolds.

The synthesis of mono- and difunctionalized [Re(η-CHR)(η-CHR)] (n = 0, 1; R = COOH, Br) complexes starting from [Re(η-benzene)] is described. The lithiation of [Re(η-benzene)] with n-BuLi leads preferentially to the neutral, alkylated product [Re(η-CH)(η-CH-Bu)] but not to the expected deprotonation of the arene ring. Deprotonation/lithiation with LDA gave the mono- and the dilithiated products in situ. Their reactions with 1,1,2,2-tetra-bromoethane (TBE) or with CO, respectively, gave [Re(η-CHBr)(η-CH)], [Re(η-CHBr)], or [Re(η-CHCOOH)(η-CH)], [Re(η-CHCOOH)]. These functionalized derivatives of [Re(η-benzene)] represent novel precursors for the synthesis of bioconjugates to bioactive structures, comparable to [Co(Cp)] or [Fe(Cp)]. Different model compounds [Re(η-CHR)(η-CHR)] (n = 0, 1; R = -SCHPh, -NHPh, -CONHCHPh, -CH-COdpa) were synthesized via amide bond formation and nucleophilic aromatic substitution. These conjugates were fully characterized including X-ray structure analyses of most products. For all complexes, the H NMR arene proton signals are strongly upfield-shifted as compared to those of the noncoordinated arenes. The electrochemical analyses show an irreversible, probably substituent-centered oxidation, which contrasts the cyclic voltammetry of the underivatized complexes where oxidation is fully reversible. The stability of the core and the reactivity of the substituents make these bis-arene complexes useful precursors in medicinal inorganic chemistry, comparable to cobaltocenium or ferrocene.