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 <b>1</b>, 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 <i>tert</i>-butyl hydroperoxide, the conversion rate is 63% and only allylic oxidation products (<i>tert</i>-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

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 <b>1</b>, 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 <i>tert</i>-butyl hydroperoxide, the conversion rate is 63% and only allylic oxidation products (<i>tert</i>-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

Heteroleptic Dysprosium(III) Single-Molecule Magnets with Amidinate and Cyclopentadienyl Ligands

Here we use a pseudoallyl ligand, N,N′-chelating amidinate (Am), together with pentamethylcyclopentadienyl (Cp*) to give two dysprosium(III) single-molecule magnets (SMMs): [{(AmiPr)DyCp*(μ-Cl)}2] and [AmdippDyCp*(Cl)(μ-Cl)Li(THF)3] with distinct energy barriers (Ueff) of 97 and 472 K, respectively. The latter Ueff value is similar to the homoleptic Cp*-based Dy-SMM