The Redox Chemistry of Some Peroxo and Superoxo Metal Ion Complexes
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The water - dioxygen cycle is a fundamental yet complex process. Important intermediates often include peroxide and superoxide. It is well established the metal ions can profoundly affect both the rate and the mechanism of this cycle, often in a catalytic manner. We have thoroughly characterized peroxo complexes in aqueous solution in order to probe the mechanistic role played by the metal ion. In effect, we start in the middle of the water - dioxygen cycle with a well defined system. The early transition metals in their highest oxidation states have been used as the metal ions for these studies. These do ions rapidly form robust peroxo and superoxo complexes. We have examined the redox chemistry of these complexes. This chemistry is compared with that of the dioxygen analogues H2O2or HO2 and HO2or O2- for the purpose of assessing in a detailed manner the role of the metal ion. In a limited sense these studies are complementary to intensive research efforts by others on such topics as the use of peroxo complexes as oxygen transfer agents in synthesis, the development of singlet oxygen generators, the utilization of dioxygen in biological systems, the search for catalysts for the oxygen electrode component of fuel cells, and decontamination procedures that use hydrogen peroxide as the oxidant.
- Physical Chemistry