Disupersilylperoxo Radical Anion [tBu sub(3)SiOOSitBu sub(3)] super(-): An Intermediate of Supersilanide Oxidation

In the oxidative process of the supersilanide anion [SitBu sub(3)] super(-), radical species are generated. The continuous wave (cw)-EPR spectrum of the reaction solution of Na[SitBu sub(3)] with O sub(2) revealed a signal, which could be characterized as disupersilylperoxo radical anion [tBu sub(3)SiOOSitBu sub(3)] super(-) affected by sodium ions though ion-pair formation. A mechanism is suggested for the oxidative process of supersilanide, which in a further step can be helpful in a better understanding of the oxidation process of isoelectronic phosphanes. The oxidative process of the supersilanide anion [SitBu sub(3)] super(-) was monitored by EPR spectroscopy. The continuous wave (cw)-EPR spectrum of the reaction solution of Na[SitBu sub(3)] and O sub(2) revealed a signal, which could be characterized as the disupersilylperoxo radical anion [tBu sub(3)SiOOSitBu sub(3)] super(-) affected by sodium ions through ion-pair formation (see scheme).