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Theoretical study of the hydroxylation of phenols mediated by an end-on bound superoxo–copper(II) complex

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Abstract

Peptidylglycine α-amidating monooxygenase and dopamine β-monooxygenase are copper-containing proteins which catalyze essential hydroxylation reactions in biological systems. There are several possible mechanisms for the reductive O2-activation at their mononuclear copper active site. Recently, Karlin and coworkers reported on the reactivity of a copper(II)–superoxo complex which is capable of inducing the hydroxylation of phenols with incorporated oxygen atoms derived from the Cu(II)-O2 ·− moiety. In the present work the reaction mechanism for the abovementioned superoxo complex with phenols is studied. The pathways found are analyzed with the aim of providing some insight into the nature of the chemical and biological copper-promoted oxidative processes with 1:1 Cu(I)/O2-derived species.

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Acknowledgments

Financial help was furnished by the Spanish Ministerio de Educación y Ciencia (MEC) projects no. CTQ2005-08797-C02-01/BQU and CTQ2008-03077/BQU and by the Catalan Department d’Universitats, Recerca i Societat de la Informació (DURSI) of the Generalitat de Catalunya project no. 2005SGR-00238. We thank Marcel Swart for valuable discussions and the reviewers for helpful comments. M.G. thanks the Spanish MEC for a Ph.D. grant.

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Authors and Affiliations

  1. Institut de Química Computacional and Departament de Química, Universitat de Girona, Campus de Montilivi, 17071, Gerona, Spain

    Mireia Güell, Josep M. Luis & Miquel Solà

  2. Department of Biochemistry and Biophysics, Stockholm University, 106 91, Stockholm, Sweden

    Mireia Güell & Per E. M. Siegbahn

Authors
  1. Mireia Güell
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  2. Josep M. Luis
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  3. Per E. M. Siegbahn
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  4. Miquel Solà
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Corresponding authors

Correspondence to Per E. M. Siegbahn or Miquel Solà.

Electronic supplementary material

Molecular orbitals of the uB3LYP/lacvp optimized triplet electronic state for the complex studied, optimized Cartesian xyz coordinates, and spin density populations for the atoms of all stationary points located on the potential energy surface for the reaction mechanism studied at the B3LYP/lacvp level of theory, together with the OPBE energies for structures 1, TS12, 2, and 3 obtained at the OPBE/cc-pvTZ(-f)&lacv3p+//B3LYP/lacvp level of theory.

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Güell, M., Luis, J.M., Siegbahn, P.E.M. et al. Theoretical study of the hydroxylation of phenols mediated by an end-on bound superoxo–copper(II) complex. J Biol Inorg Chem 14, 273–285 (2009). https://doi.org/10.1007/s00775-008-0447-7

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  • DOI: https://doi.org/10.1007/s00775-008-0447-7

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