SYNTHESIS, REACTIVITIES AND ELECTROCHEMISTRY OF TRANS-DIOXO-RUTHENIUM(VI) COMPLEXES OF PI-AROMATIC DIIMINES

被引：27

作者：

CHE, CM

LEUNG, WH

LI, CK

POON, CK

机构：

来源：

JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS | 1991年 / 03期

关键词：

D O I：

10.1039/dt9910000379

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The synthesis and electrochemistry of trans-[RuIII(L)2(OH)(H2O)][ClO4]2 [L = 1,10-phenanthroline (phen) or 5,5'-dimethyl-2,2'-bipyridine(dmbipy)] are described. Oxidation of trans-[RuIII(L)2(OH)-(H2O)]2+ by Ce(IV) in water gave trans-[Ru(VI)(L)2O2]2+ which were isolated as the yellow perchlorate salts. The complex trans-[Ru(VI)(dmbipy)2O2][ClO4]2 is a powerful oxidant with E(o)(Ru(VI)-Ru(IV)) = 1.0 V vs. saturated calomel electrode at pH 1.0. In acetonitrile or acetone, it oxidizes alcohols to ketones/aldehydes, tetrahydrofuran to gamma-butyrolactone, alkenes to epoxides and saturated or aromatic hydrocarbons to alcohols/ketones. Oxidation of saturated alkanes occurs preferentially at the tertiary C-H bond. In the presence of CCl4, cyclohexane is oxidized to cyclohexyl chloride instead of cyclohexanone. The mechanisms of alcohol and cyclohexane oxidation were investigated by kinetic experiments and by isotope labelling studies.

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页码：379 / 384

页数：6

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