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Article Dans Une Revue Journal of Computational Chemistry Année : 2011

Spin-driven activation of dioxygen in various metalloenzymes and their inspired models.

Anthony Scemama
Julien Pilme
Olivier Parisel
Helene Gerard
Michel Caffarel
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Résumé

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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Dates et versions

hal-00992047 , version 1 (29-01-2020)

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Aurelien de La Lande, Dennis R Salahub, Jacques Maddaluno, Anthony Scemama, Julien Pilme, et al.. Spin-driven activation of dioxygen in various metalloenzymes and their inspired models.. Journal of Computational Chemistry, 2011, 32 (6), pp.1178-1182. ⟨10.1002/jcc.21698⟩. ⟨hal-00992047⟩
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