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How to optimize a CH cleavage with a mononuclear copper–dioxygen adduct?
Author(s) -
De La Lande A.,
Gérard H.,
Parisel O.
Publication year - 2008
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.21679
Subject(s) - adduct , chemistry , peroxide , superoxide , copper , bond cleavage , photochemistry , pseudopotential , ligand (biochemistry) , cleavage (geology) , stereochemistry , polymer chemistry , catalysis , organic chemistry , materials science , physics , enzyme , condensed matter physics , biochemistry , receptor , fracture (geology) , composite material
We here report the investigations on the role of the charge transfer (CT) from copper toward dioxygen on the activation barrier of the CH bond breaking in a model [Cu(trenCH 3 )(O 2 )] + adduct. By playing on the donating capability of the trenCH 3 ligand, by means of a supplementary pseudopotential applied on the apical nitrogen atom, the existence of an optimum CT to achieve the rupture of the CH bond is revealed. When considering the dioxygen/superoxide/peroxide range in its whole, it appears that both dioxygen‐ and peroxide‐type complexes are poor oxidant toward the CH bond. At variance, superoxide dominant complexes are confirmed to be better suited for a reactive purpose. © 2008 Wiley Periodicals, Inc. Int J Quantum Chem, 2008