Photochemistry of the permanganate ion in low-temperature frozen matrices

Inorganic Chemistry
Wyatt A Thornley, Thomas E Bitterwolf

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(η(2)-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(η(2)-O2)(-) does not lose O2 thermally or photochemically and is not an intermediate in the photodecomposition reaction. A mechanism is proposed in which MnO2(η(2)-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.

References

May 22, 2003·Journal of Computational Chemistry·E Van Lenthe, E J Baerends
Jul 13, 2006·The Journal of Physical Chemistry. a·Johannes NeugebauerMarcel Nooijen
Mar 4, 2011·Journal of Computational Chemistry·Stefan GrimmeLars Goerigk

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Citations

Apr 28, 2020·Physical Chemistry Chemical Physics : PCCP·Omer S HaggagSanford Ruhman
Mar 27, 2021·Water Science and Technology : a Journal of the International Association on Water Pollution Research·Miaomiao YeRong Chen

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