Manganese 1,4,7-trimethyl-1,4,7-triazacyclononane complexes: Versatile catalysts for the oxidation of organic compounds with hydrogen peroxide

被引：50

作者：

Smith, John R. Lindsay ^{[1
]}

Gilbert, Bruce C.

Payeras, Antoni Mairata i

Murray, Jane

Lowdon, Terry R.

Oakes, John

Prats, Roger Pons i

Walton, Paul H.

机构：

[1] Univ York, Dept Chem, York YO10 5DD, N Yorkshire, England

[2] C6 Solut Ltd, Castleford WF10 2JT, W Yorkshire, England

[3] Unilever Res, Port Sunlight Labs, Merseyside L63 3JW, England

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 2006年 / 251卷 / 1-2期

关键词：

oxidation; hydrogen peroxide; catalysis; manganese; 1,4,7-trimethyl-1,4,7-triazacyclononane;

D O I：

10.1016/j.molcata.2006.02.025

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：

The oxidation of phenols, cinnamic acids and methyl aryl sulfides by hydrogen peroxide, using three catalyst systems, [L2Mn2IV(mu-O)(3)](PF6)(2), L=1,4,7-trimethyl-1,4,7-triazacyclononane; [LMnIV(OMe)(3)(PF6); and Mn-II/L/H2O2, have been studied. The results from a combination of spectroscopic and kinetic studies, coupled with Hammett correlations and O-18 labelling experiments, suggest that with each system the active oxidant is an electrophilic, mononuclear oxo-manganese (V) species. The influence of additives that can act as co-ligands for the manganese species has been investigated, with a view to controlling the activity/selectivity of the active oxidant. The two-step, sulfide-sulfoxide-sulfone, oxidation shows an unusual switch in the philicity of the active oxidant from electrophilic in the first step to nucleophilic in the second. Mechanisms for the oxidations are proposed. (c) 2006 Elsevier B.V. All rights reserved.

引用

页码：114 / 122

页数：9

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