Synthesis, structure, and reactivity of dirhodium(II) complexes bearing a tetramethylcyclopentadienyl-bipyridine ligand

Abstract A novel dirhodium complex bearing a tetramethylcyclopentadienyl-pyridine (Me4Cp-bpy) as a bridging ligand was synthesized and characterized. The complex is composed of two electronically differentiated Rh centers, and its photophysical and redox properties were investigated by UV–Vis absorption, cyclic voltammetry, and theoretical calculations. Facile generation of a cis-coordination site at the Rh–Rh bond was realized, enabling aerobic oxidation to yield a dirhodium oxo complex. These findings provide a new design for paddlewheel dirhodium complexes potentially capable of cooperative molecular activation and transformations at the Rh–Rh bond.