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Stabilized with an N‐heterocyclic carbene ligand of the smallest steric profile, PdII(η2‐O2)(IMe)2 (IMe = 1,3‐dimethylimidazole‐2‐ylidene) was synthesized by the direct addition of dioxygen to Pd0(IMe)2. The peroxidopalladium complex with IMe, which was previously available only by computation, was characterized by IR spectroscopy and X‐ray crystallography. Moreover, its oxygen‐atom‐transfer reactivity...
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