Spectroscopic and computational characterization of CuII-OOR (R = H or cumyl) complexes bearing a Me6-tren ligand

被引：41

作者：

Choi, Yu Jin ^{[1
]}

Cho, Kyung-Bin ^{[2
]}

Kubo, Minoru ^{[3
]}

Ogura, Takashi ^{[3
]}

Karlin, Kenneth D. ^{[2
,4
]}

Cho, Jaeheung ^{[1
]}

Nam, Wonwoo ^{[1
,2
]}

机构：

[1] Ewha Womans Univ, Dept Chem & Nano Sci, Seoul 120750, South Korea

[2] Ewha Womans Univ, Dept Bioinspired Sci, Seoul 120750, South Korea

[3] Univ ofHyogo, Grad Sch Life Sci, Picobiol Inst, Hyogo 6781297, Japan

[4] Johns Hopkins Univ, Dept Chem, Baltimore, MD 21218 USA

来源：

DALTON TRANSACTIONS | 2011年 / 40卷 / 10期

关键词：

D O I：

10.1039/c0dt01036g

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

A copper(II)-hydroperoxo complex, [Cu(Me-6-tren)(OOH)](+) (2), and a copper(II)-cumylperoxo complex, [Cu(Me-6-tren)(OOC(CH3)(2)Ph)](+) (3), were synthesized by reacting [Cu(Me-6-tren)(CH3CN)](2+) (1) with H2O2 and cumyl-OOH, respectively, in the presence of triethylamine. These intermediates, 2 and 3, were successfully characterized by various physicochemical methods such as UV-vis, ESI-MS, resonance Raman and EPR spectroscopies, leading us to propose structures of the Cu(II)-OOR species with a trigonal-bipyramidal geometry. Density functional theory (DFT) calculations provided geometric and electronic configurations of 2 and 3, showing trigonal bipyramidal copper(II)-OOR geometries. These copper(II)-hydroperoxo and -cumylperoxo complexes were inactive in electrophilic and nucleophilic oxidation reactions.

引用

页码：2234 / 2241

页数：8

共 79 条

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