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Spin‐driven activation of dioxygen in various metalloenzymes and their inspired models
Author(s) -
De La Lande Aurelien,
Salahub Dennis R.,
Maddaluno Jacques,
Scemama Anthony,
Pilme Julien,
Parisel Olivier,
Gerard Helene,
Caffarel Michel,
Piquemal JeanPhilip
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21698
Subject(s) - chemistry , singlet state , spin (aerodynamics) , lone pair , spin states , triplet state , ground state , adduct , topology (electrical circuits) , electron localization function , photochemistry , chemical physics , computational chemistry , molecule , electron , excited state , atomic physics , physics , organic chemistry , inorganic chemistry , quantum mechanics , mathematics , combinatorics , thermodynamics
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. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2011
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