Synthesis, reactivities and electrochemistry of trans-dioxoruthenium(VI) complexes of π-aromatic diimines
- 1 January 1991
- journal article
- research article
- Published by Royal Society of Chemistry (RSC) in J. Chem. Soc., Dalton Trans.
- No. 3,p. 379-384
- https://doi.org/10.1039/dt9910000379
Abstract
The synthesis and electrochemistry of trans-[RuIII(L)2(OH)(H2O)][CIO4]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 CeIV in water gave trans-[RuVI(L)2O2]2+ which were isolated as the yellow perchlorate salts. The complex trans-[RuVI(dmbipy)2O2][CIO4]2 is a powerful oxidant with E°(RuVI–RuIV)= 1.0 V vs. saturated calomel electrode at pH 1.0. In acetonitrile or acetone, it oxidizes alcohols to ketones/aldehydes, tetrahydrofuran to γ-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.Keywords
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