O2 Activation and Selective Phenolate ortho Hydroxylation by an Unsymmetric Dicopper μ-η1:η1-Peroxido Complex


  • This work was supported financially by MCYT of Spain (projects CTQ2006-05367/BQU and CTQ2009-08464/BQU to M.C.), by the U.S. NIH (grant GM38767 to L.Q.), and by the Italian MIUR (Prin project to L.L.). I.G.B and A.C. thank MICINN for PhD grants. M.T.-S. thanks the CSIC for the JAE-DOC contract. We thank STR-UdG for technical support. M.C. also thanks the Generalitat Catalunya for an ICREA-Academia award and for project 2009 SGR-637.


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Unusual reactivity: A novel unsymmetric dicopper complex gives rise to the unsymmetric species 1-O2 having a μ-η11-O2 binding mode and reactivity patterns not previously observed for symmetric analogues. It is unreactive in oxygen atom transfer reactions, but it can selectively bind phenolate and mediate its ortho hydroxylation, thereby demonstrating a conceptually different tyrosinase model with exquisite selectivity.