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Quantum Chemical Studies on Metal-Oxo Species Related to the Mechanisms of Methane Monooxygenase and Photosynthetic Oxygen Evolution

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Book cover Metal-Oxo and Metal-Peroxo Species in Catalytic Oxidations

Part of the book series: Structure and Bonding ((STRUCTURE,volume 97))

Abstract

During the last few years it has become possible to study enzymatic mechanisms by means of high accuracy quantum chemistry methods. In the present review, examples are given of applications of density functional theory to two mechanisms involving redox active centers. In methane monooxygenase an iron dimer complex oxidizes methane to methanol. A hydrogen abstraction mechanism is suggested involving a high-valent Fe(IV,IV) intermediate, termed Q. In Photosystem II an oxyl radical mechanism is suggested for the formation of O2. Different models of the oxygen evolving cluster are discussed. Spin-state considerations are emphasized.

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Author information

Authors and Affiliations

  1. Department of Physics, Stockholm University, Box 6730, S-113 85, Stockholm, Sweden

    P. E. M. Siegbahn

  2. Yale Chemistry Department, PO Box 208107, 225 Prospect St., New Haven, CT, 06520-8107, USA

    Robert H. Crabtree

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  1. P. E. M. Siegbahn
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  2. Robert H. Crabtree
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Editors and Affiliations

  1. Laboratoire de Chimie de Coordination du CNRS, 205 route de Narbonne, 31077, Toulouse Cedex 4, France

    Bernard Meunier

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Siegbahn, P.E.M., Crabtree, R.H. (2000). Quantum Chemical Studies on Metal-Oxo Species Related to the Mechanisms of Methane Monooxygenase and Photosynthetic Oxygen Evolution. In: Meunier, B. (eds) Metal-Oxo and Metal-Peroxo Species in Catalytic Oxidations. Structure and Bonding, vol 97. Springer, Berlin, Heidelberg. https://doi.org/10.1007/3-540-46592-8_5

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  • DOI: https://doi.org/10.1007/3-540-46592-8_5

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  • Print ISBN: 978-3-540-66943-2

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