Sc3+ (or HClO4) Activation of a Nonheme FeIII-OOH Intermediate for the Rapid Hydroxylation of Cyclohexane and Benzene

Abstract

[Fe(β-BPMCN)(CH₃CN)₂]²⁺ (1, BPMCN = N,N' -bis(pyridyl-2-methyl)- N,N' -dimethyl- trans-1,2-diaminocyclo-hexane) is a relatively poor catalyst for cyclohexane oxidation by H₂O₂ and cannot perform benzene hydroxylation. However, addition of Sc³⁺ activates the 1/H₂O₂ reaction mixture to be able to hydroxylate cyclohexane and benzene within seconds at -40 °C. A metastable S = 1/2 Fe^III-(η¹-OOH) intermediate 2 is trapped at -40 °C, which undergoes rapid decay upon addition of Sc³⁺ at rates independent of [substrate] but linearly dependent on [Sc³⁺]. HClO₄ elicits comparable reactivity as Sc³⁺ at the same concentration. We thus postulate that these additives both facilitate O-O bond heterolysis of 2 to form a common highly electrophilic Fe^V═O oxidant that is comparably reactive to the fastest nonheme high-valent iron-oxo oxidants found to date.