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

نویسندگان

  • Aurélien de la Lande
  • Dennis R. Salahub
  • Jacques Maddaluno
  • Anthony Scemama
  • Julien Pilmé
  • Olivier Parisel
  • Helene Gerard
  • Michel Caffarel
  • Jean-Philip Piquemal
چکیده

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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عنوان ژورنال:
  • Journal of computational chemistry

دوره 32 6  شماره 

صفحات  -

تاریخ انتشار 2011