Redox-Active Cobalt(II/III) Metal-Organic Framework for Selective Oxidation of Cyclohexene

We report herein a new cobalt(II/III) mixed-valence metal-organic framework formulated as [Co^IICo₂^III(μ₃-O)(bdc)₃(tpt)]·guest 1, where bdc = benzene-1,4-dicarboxylate and tpt = 2,4,6-tri(4-pyridinyl)-1,3,5-triazine, which can be used as a redox-active heterogeneous catalyst for selective oxidation of cyclohexene on the allylic position without destroying the adjacent double bond. Two oxidants were chosen to demonstrate this result. For using tert-butyl hydroperoxide, the conversion rate is 63% and only allylic oxidation products (tert-butyl-2-cyclohexenyl-1-peroxide, 86%; 2-cyclohexen-1-one, 14%) are found, whereas if using O₂ as oxidant, a total conversion of 38% is achieved and also only the allylic oxidation products (cyclohexenyl hydroperoxide, 72%; 2-cyclohexen-1-one, 20%; and cyclohex-2-en-1-ol, 8%) are found. The absence of any adduct on the double bond may be due to the unique radical chain mechanism triggered by the mixed-valent [Co^IICo₂^III(μ₃-O)] centers.