Theoretical Investigation of Dioxygen Activation and Hydrocarbon Oxidation Catalysed by Bioinspired Metal-Organic Frameworks.

Dioxygen activation by a bioinspired FeZn4(prv)4(btdd)3 MOF to form high-spin (S = 2) iron(IV)-oxo active species was revealed to proceed via two-state reactivity. The iron(IV)-oxo species containing the Lewis acid Zn2+ cation hydroxylates cyclohexane with an energy barrier of only 15.1 kcal mol-1, which is reminiscent of the indispensable role of the Ca2+ ion in the PSII system.