ELECTROCATALYTIC OLEFIN EPOXIDATION USING MANGANESE SCHIFF-BASE COMPLEXES AND DIOXYGEN

被引：96

作者：

HORWITZ, CP ^{[1
]}

CREAGER, SE ^{[1
]}

MURRAY, RW ^{[1
]}

机构：

[1] UNIV N CAROLINA,DEPT CHEM,CHAPEL HILL,NC 27599

来源：

INORGANIC CHEMISTRY | 1990年 / 29卷 / 05期

关键词：

D O I：

10.1021/ic00330a021

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Electrochemical reduction of [MnIII(salen)]+ (salen = N,N′-ethylenebis(salicylaldiminato)) complexes in acetonitrile solution in the presence of benzoic anhydride, l-methylimidazole, dioxygen, and an olefin yields the epoxide of the olefin in as much as 48% yield based on electrochemical charge passed. Cyclic voltammetric and rotating-disk voltammetric results are consistent with an electron/dioxygen bonding/electron (ECE) reaction sequence to produce a manganese-peroxo complex in which the O–O bond is subsequently heterolyzed by reaction with benzoic anhydride to yield a Mn(V)-oxo complex. Cis/trans kinetic competition experiments with cis-cyclooctene and trans-2-octene give a cis/trans reactivity ratio of 10 for the electrolytic epoxidation. Iodosylbenzene gives a ratio of 14 under comparable conditions. Electrolysis in the presence of cyclohexene yields primarily cyclohexene oxide and significant quantities of the allylic oxidation products 2-cyclohexen-1-one and 2-cyclohexen-1-ol. © 1990, American Chemical Society. All rights reserved.

引用

页码：1006 / 1011

页数：6

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[2]

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