ABSTRACT
The syntheses and characterization of a series of binuclear cobalt complexes of the octadentate Schiff-base calixpyrrole ligand L are described. The cobalt(II) complex [Co(2)(L)] was prepared by a transamination method and was found to adopt a wedged, Pac-man geometry in the solid state and in solution. Exposure of this compound to dioxygen resulted in the formation of a 90:10 mixture of the peroxo [Co(2)(O(2))(L)] and superoxo [Co(2)(O(2))(L)](+) complexes in which the peroxo ligand was found to bind in a Pauling mode in the binuclear cleft in pyridine and acetonitrile adducts in the solid state. The dioxygen compounds can also be prepared directly from Co(OAc)(2) and H(4)L under aerobic conditions in the presence of a base. The reduction of dioxygen catalyzed by this mixture of compounds was investigated using cyclic voltammetry and rotating ring disk electrochemistry and, in acidified ferrocene solutions, using UV-vis spectrophotometry, and although no formation of peroxide was seen, reaction rates were slow and had limited turnover. The deactivation of the catalyst material is thought to be due to a combination of the formation of stable hydroxy-bridged binuclear complexes, for example, [Co(2)(OH)(L)](+), an example of which was characterized structurally, and the catalytic resting point, the superoxo cation, is formed by a pathway independent of the major peroxo product. Collision-induced dissociation mass spectrometry experiments showed that, while [Co(2)(O(2))(L)]H(+) ions readily lose a single O atom, the resulting Co-O(H)-Co core remains resistant to further fragmentation. Furthermore, DFT calculations show that the O-O bond distance in the dioxygen complexes is not a good indicator of the degree of reduction of the O(2) unit and provide a reduction potential of ca. +0.40 V versus the normal hydrogen electrode for the [Co(2)(O(2))(L)](+/0) couple in dichloromethane solution.
