Catalytic Properties of Cobalt(III)-Oxo Cubanes in the TBHP Oxidation of Benzylic Alcohols

Two series of oxo-bridged Co(III) complexes of the type Co(4)O(4)(O(2)CC(6)H(4)-X)(4)(py)(4) (1) and Co(4)O(4)(O(2)CC(6)H(4)-X)(4)(4-Mepy)(4) (2), where X = H (a), Me (b), MeO (c), Cl (d), NO(2) (e), have been synthesized and characterized in detail. The molecular structures of the complexes consist of a cubelike Co(4)(mu(3)-O)(4) core having Co and O atoms at alternate vertices with carboxylato ligands bridging the Co(3+) ions along four face diagonals of the approximate cube. Nitrogen atoms from pyridyl ligands complete the distorted-octahedral coordination around each Co(III). These neutral Co(III) complexes undergo a nearly reversible one-electron oxidation involving the redox couple [Co(4)(III)(mu(3)-O)(4)](4+) <-> [Co(3)(III)Co(IV)(mu(3)-O)(4)](5+) at potentials (similar to 0.7-1.0 V) that linearly depend on the electronic influence of X, The cobalt(III) clusters of types 1 and 2 have been found to effectively promote the TBHP oxidation of benzylic alcohols under homogeneous conditions to produce the corresponding carbonyl compounds,