A Cobalt(II)‐containing Metal‐Organic Framework Showing Catalytic Activity in Oxidation Reactions

A metal‐organic framework (MOF) containing redox active CoII atoms, [CoII(BPB)]·3DMF (1), has been prepared from the solvothermal reaction of CoII nitrate and 1,4‐bis(4′‐pyrazolyl)benzene (H2‐BPB) in dimethylformamide (DMF). Compound 1 constitutes a porous coordination framework that is built up by interconnecting 1D CoII polymer chains with (BPB)2− ligands. The thermal stability of 1 was investigated by thermogravimetric (TG) analysis and variable‐temperature X‐ray powder diffraction (VTXRPD), which indicate that the framework of 1 is stable upon removal of solvent molecules. The argon adsorption isotherm of 1 at 77 K indicates a porous structure with a BET surface area of 1207 m2/g. As a test reaction for catalytic activity of 1, the oxidation of cyclohexene was examined employing tert‐butyl hydroperoxide as oxidant. The maximum substrate conversion achieved after 12 h was 62 % with an estimated turn‐over number (TON) of 44 based on the number of converted substrate molecules (cyclohexene) per CoII atom.