Spin-driven activation of dioxygen in various metalloenzymes and their inspired models |
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Authors: | de la Lande Aurelien Salahub Dennis R Maddaluno Jacques Scemama Anthony Pilme Julien Parisel Olivier Gerard Helene Caffarel Michel Piquemal Jean-Philip |
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Affiliation: | Department of Chemistry and Institute for Biocomplexity and Informatics, University of Calgary, 2500 University Drive NW, Calgary, Alberta, Canada T2N 1N4. aurelien.de-la-lande@u-psud.fr |
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Abstract: | Although potentially powerful, molecular oxygen is an inert oxidant due to the triplet nature of its ground state. Therefore, many enzymesse various metal cations (M) to produce singlet active species M(n) O(2) . In this communication we investigate the topology of the Electron Localization Function (ELF) within five biomimetic complexes which are representative of the strategies followed by metalloenzymes to activate O(2) . Thanks to its coupling to the constrained DFT methods the ELF analysis reveals the tight connection between the spin state of the adduct and the spatial organization of the oxygen lone pairs. We suggest that enzymes could resort to spin state control to tune the regioselectivity of substrate oxidations. |
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Keywords: | enzyme spin electron localization DFT constrained DFT |
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