A Robust Mn Catalyst for H2O2 Disproportionation in Aqueous Solution

被引:22
|
作者
Lee, Wei-Tsung [1 ]
Xu, Song [1 ]
Dickie, Diane A. [2 ]
Smith, Jeremy M. [1 ]
机构
[1] New Mexico State Univ, Dept Chem & Biochem, Las Cruces, NM 88003 USA
[2] Univ New Mexico, Dept Chem & Chem Biol, Albuquerque, NM 87131 USA
关键词
Manganese; Reaction mechanisms; Peroxides; Homogeneous catalysis; Macrocycles; ELECTRON-PARAMAGNETIC-RESONANCE; HYDROGEN-PEROXIDE; MANGANESE(IV) COMPLEX; CATALASE ACTIVITY; METHYLENE-BLUE; MIMICS; ANTIOXIDANTS; EPOXIDATION; REACTIVITY; LIGANDS;
D O I
10.1002/ejic.201300184
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The pyridinophane complex [Mn(Py2N2)(H2O)(2)](2+) catalyses the disproportionation of H2O2 in aqueous solution over a wide pH range. Kinetic investigations reveal an induction period, which is proposed to involve the formation of a hydroperoxo intermediate, as well as evidence for catalyst self-inhibition. A catalytic cycle involving mononuclear intermediates has been proposed. Spectroscopic investigations under turnover conditions are consistent with this proposal and show that the resting state of the catalyst is a mononuclear Mn-II complex. The robustness of the catalyst is evidenced by its ability to achieve turnover numbers of 58000 in aqueous solution.
引用
收藏
页码:3867 / 3873
页数:7
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