Bicyclic pyrazabole-bridged ferrocenes with BH groups at their bridgehead positions were prepared from [Li(thf)]2[1,1’-fc(BH3)2] and pyrazole or 3,5-dimethylpyrazole in the presence of Me3SiCl (1 or 1Me, respectively; 1,1’-fc = ferrocenylene);...

Ansa-ferrocenes with pyrazabole bridges are chemically robust entities and therefore suitable building blocks for the synthesis of rigid-rod polymers that combine redox-active Fe(II) centers and beltene-like  faces. The specific monomers we developed bear OEt groups at both tetracoordinated boron atoms (for solubility reasons) and ethynyl substituents at the 4-positions of the two pyrazole rings. Polymerization was accomplished by a condensation reaction with 1,4-diiodobenzene using a Sonogashira-Hagihara-type protocol. Thereby, oligomers with a number-average molecular weight of Mn = 7.6 kDa and dispersity of Ð = 1.55 were obtained, suggesting an average chain length of about 14 repeating units based on gel permeation chromatography (GPC) analysis in THF relative to narrow polystyrene standards. The molecular-weight determination was complemented by MALDI-TOF mass spectrometry and (heteronuclear) NMR spectroscopy to verify the intact pyrazabole monomer repeat units and the nature of the end-groups. The oligomers were further characterized by UV−vis spectroscopy and cyclic voltammetry, which demonstrated the successful synthesis of a new class of redox-active materials.