| Abstract
| - Compared to the system in aqueous solution, the equilibrationreactions in acetonitrile between MTO and themethylrhenium peroxidesCH3ReO2(η2-O2)(A) andCH3ReO(η2-O2)2(H2O)(B) are slower but more favoredthermodynamically. In CH3CN, small concentrationsof water facilitate the formation of A (especially) andB.These species decompose to methyl hydroperoxide and perrhenic acidin CD3CN, rather than to methanol andperrhenic acid as in aqueous solution. The proposed mechanisminvolves the intramolecular migration of themethyl group to a peroxo oxygen, followed by hydrolysis, and it isfacilitated by photolysis. The potential useof B as photocatalyst does not seem promising,however.
- The compoundCH3ReO(η2-O2)2(H2O)decomposes to perrhenic acid along different pathways in organic andaqueous media. The formation of CH3OOH inacetonitrile is facilitated byirradiation.
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