1. Spin-driven activation of dioxygen in various metalloenzymes and their inspired models.
- Author
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De La Lande, Aurelien, Salahub, Dennis R., Maddaluno, Jacques, Scemama, Anthony, Pilme, Julien, Parisel, Olivier, Gerard, Helene, Caffarel, Michel, and Piquemal, Jean-Philip
- Subjects
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ACTIVATION (Chemistry) , *OXYGEN , *METALLOENZYMES , *OXIDIZING agents , *CATIONS , *METAL ions , *BIOMIMETIC chemicals , *MOLECULE-molecule collisions - 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 MO. 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. 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. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011 [ABSTRACT FROM AUTHOR]
- Published
- 2011
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