High-valent manganese in polyoxotungstates .4. Catalytic and stoichiometric alkene oxidation

被引：29

作者：

Zhang, XY ^{[1
]}

Pope, MT ^{[1
]}

机构：

[1] GEORGETOWN UNIV,DEPT CHEM,WASHINGTON,DC 20057

来源：

JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL | 1996年 / 114卷 / 1-3期

关键词：

heteropolytungstates; manganese(III; IV); dimanganese(III; III); tetramanganese(II; iodosylbenzene; epoxidation; cyclohexene; stilbene; cis/trans isomerization;

D O I：

10.1016/S1381-1169(96)00318-4

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：

Six manganese-containing heteropolytungstates, alpha-[(XO(4))W11MnO36](n-) (XW(11)Mn; X=P, Si, B, and Zn), gamma-[(SiO4)(W10Mn2O36H6)-O-III](4-)(SiW10Mn2), and [Mn-4(II)(H2O)(2)(PW9O34)(3)](10-) (P2W18Mn4) have been compared as catalysts for the oxidation of cyclohexene and cis-stilbene by iodosylbenzene. The yield of epoxide and the cis/trans isomer ratio of stilbene epoxides are dependent upon the charge of the XW(11)Mn catalysts. In addition to the oxidation reactions, isomerization of cis-stilbene to trans-stilbene was observed when an oxidized derivative of P2W18Mn4 was used as a catalyst. Stoichiometric oxidation of cyclohexene or cis-stilbene by high-oxidation-state manganese-substituted heteropolyanions eropolyanions was also examined. Product distributions from stoichiometric oxidation are different from those from the catalytic reactions for each heteropolyanion, suggesting that different reaction pathways may be involved in these two types of reactions.

引用

页码：201 / 208

页数：8

共 35 条

[1]

BACKVALL JE, 1992, J AM CHEM SOC, V114, P534

[2]

CASTELLINO AJ, 1988, J AM CHEM SOC, P1313

[3]

DEMONTELLANO PRO, 1987, J BIOL CHEM, V262, P11641

[4] SUSTAINED CATALYTIC HOMOGENOUS OXO-TRANSFER OXIDATION OF ALKANES - INTERACTION OF ALKYL HYDROPEROXIDES WITH TRANSITION METAL-SUBSTITUTED POLYOXOMETALATES [J].