How to optimize a C-H cleavage with a mononuclear copper-dioxygen adduct?

被引：19

作者：

De La Lande, A. ^{[1
,2
]}

Gerard, H. ^{[1
,2
]}

Parisel, O. ^{[1
,2
]}

机构：

[1] Univ Paris 06, UPMC, Chim Theor Lab, UMR 7616, F-75005 Paris, France

[2] CNRS, Chim Theor Lab, UMR 7616, F-75005 Paris, France

来源：

INTERNATIONAL JOURNAL OF QUANTUM CHEMISTRY | 2008年 / 108卷 / 11期

关键词：

biomimetic chemistry; spin-flip TDDFT; CH cleavage; dioxygen activation; charge transfer;

D O I：

10.1002/qua.21679

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

We here report the investigations on the role of the charge transfer (CT) from copper toward dioxygen on the activation barrier of the C-H 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 C-H 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 C-H bond. At variance, superoxide dominant complexes are confirmed to be better suited for a reactive purpose. (c) 2008 Wiley Periodicals, Inc.

引用

页码：1898 / 1904

页数：7

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