Axial Redox Tuning at a Tetragonal Cobalt Center.

Square pyramidal cobalt complexes were prepared to study their multielectron redox properties. To build a stable redox-active cobalt complex, the combination of a tridentate acriPNP (acriPNP- = 4,5-bis(diisopropylphosphino)-2,7,9,9-tetramethyl-9H-acridin-10-ide) ligand with a bidentate ligand, such as 2,2'-bipyridine, 2-(o-phenyl)pyridine, biphenylene, and their analogues, was employed. In a cobalt complex having a tetragonal structure, the dx2-y2 orbital possesses an antibonding character and must remain empty for its structural integrity, while the dz2 orbital acts as a redox-active frontier molecular orbital (FMO). Tuning the redox potential of the Co(II/I) couple was successfully achieved by introducing a different axial donor. The reduction of Co(II) to Co(I) occurs at -2.6 V for a neutral donor but shifts to -3.4 V for an anionic donor. Since the redox-active dz2 orbital is close in energy to other ligand-based orbitals, multielectron redox activity is also observed. Electrochemical measurements indicate three reversible redox events within a window of -3.0-0.0 V vs Fc/Fc+ in tetrahydrofuran (THF). These redox processes are fully reversible for over 100 cycles, reflecting the electrochemical stability of these cobalt complexes. Surprisingly, the oxidation potential of the acriPNP ligand varies dramatically from +0.15 to -2.4 V, which is probably due to the cobalt contribution on the amido-based molecular orbital. The electronic structure of the cobalt complexes was examined structurally, spectroscopically, and theoretically.