Photochemistry of the Permanganate Ion in Low-Temperature Frozen Matrices

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Abstract
Photolysis of the permanganate anion, MnO4–, in tetralkylammonium tetrafluoroborate matrices at 85 K results in formation of a single product, the metastable manganese(V) peroxo complex MnO2(η2-O2)−. Although previously unobserved, this peroxo species has been postulated to be an intermediate in the photodecomposition of permanganate, yielding O2 and MnO2–. Results from variable-temperature and intensity-dependence photolysis experiments in solution, however, suggest that MnO2(η2-O2)− does not lose O2 thermally or photochemically and is not an intermediate in the photodecomposition reaction. A mechanism is proposed in which MnO2(η2-O2)− is formed through vibrational relaxation of an excited [MnO4–]* species, which may also follow an alternative relaxation pathway that results in the formation of MnO2– and O2 photodecomposition products.

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