Bismuth–ferrocene carboxylates: synthesis and structure

Abstract

The reaction of ferrocenedicarboxylic acid with triphenylbismuth in a 1 : 1 ratio under solvothermal conditions afforded the 1D coordination polymer [Bi(2)(μ(2)-η(2)-OOCFcCOO-μ(2)-η(2))(η(2)-OOCFcCOO-η(2))(μ(2)-η(2)-OOCFcCOO-η(2))](n) (1). In this polymer two types of bismuth centers (hepta- and octacoordinate) are present and are interconnected by the bridging coordination of ferrocene dicarboxylate ligands. The reaction of ferrocenecarboxylic acid with triphenylbismuth in a 1 : 3 ratio, in toluene, under refluxing conditions, afforded the 1D coordination polymer [Bi(μ(2)-η(2)-FcCOO)(η(2)-FcCOO)(2)](n) (2). In the solid state, 2 exists as a helical polymer, where the inner bismuth chain is enclosed by an external sheath of ferrocene carboxylate ligands. In solution, however, 2 decomposes into the monomeric repeat unit [Bi(FcCOO)(3)] which is indicated by ESI-MS as well as cyclic voltammetric studies. Thus, a single, quasi-reversible redox event is seen for 2 in solution. The reaction of triphenylbismuth with ferrocenecarboxylic acid in a 1 : 1 stoichiometry afforded the molecular dimer [Bi(2)(μ(2)-η(2)-FcCOO)(2)(η(2)-FcCOO)(4)(H(2)O)(4)]·(2FcCOOH) (3). Compounds 1-3 reveal rich supramolecular architectures in the solid state as a result of the presence of C-H···O, C-H···π and π···π interactions.