Controlling the Reactivity of Copper(II) Acylperoxide Complexes.

The redox state of the metallomonooxygenases is finely tuned by imposing specific coordination environments on the metal center to reduce the activation energy for the generation of active-oxygen species and subsequent substrate oxygenation reactions. In this study, copper(II) complexes supported by a series of linear tetradentate ligands consisting of a rigid 6-, 7-, or 8-membered cyclic diamine with two pyridylmethyl (-CH2Py) side arms (L6Pym2, L7Pym2, and L8Pym2) are employed to examine the effects of the coordination environment on the reactivity of their acylperoxide adduct complexes. The UV-vis and electron paramagnetic resonance spectroscopic data indicate that the ligand-field splitting between the dx2-y2 and dz2 orbitals of the starting copper(II) complexes increase with an increase of the ring size of the diamine moiety (L6Pym2 → L7Pym2 → L8Pym2). In the reaction of these copper(II) complexes with m-chloroperbenzoic acid (m-CPBA), the L6Pym2 complex gives a stable m-CPBA adduct complex, whereas the L7Pym2 and L8Pym2 complexes are immediately converted to the corresponding m-chlorobenzoic acid (m-CBA) adducts, indicating that the reactivity of the copper(II) acylperoxide complexes largely depends on the coordination environment induced by the supporting ligands. Density functional theory (DFT) calculations on the m-CPBA adduct complexes show that the ligand-field-splitting energy increases with an increase of the ring size of the diamine moiety, as in the case of the starting copper(II) complexes, which enhances the reactivity of the m-CPBA adduct complexes. The reasons for such different reactivities of the m-CPBA adduct complexes are evaluated by using DFT calculations.