Disupersilylperoxo Radical Anion [tBu3SiOOSitBu3]⋅−: An Intermediate of Supersilanide Oxidation

In the oxidative process of the supersilanide anion [SitBu3]−, radical species are generated. The continuous wave (cw)‐EPR spectrum of the reaction solution of Na[SitBu3] with O2 revealed a signal, which could be characterized as disupersilylperoxo radical anion [tBu3SiOOSitBu3]⋅− 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 [SitBu3]− was monitored by EPR spectroscopy. The continuous wave (cw)‐EPR spectrum of the reaction solution of Na[SitBu3] and O2 revealed a signal, which could be characterized as the disupersilylperoxo radical anion [tBu3SiOOSitBu3]⋅− affected by sodium ions through ion‐pair formation (see scheme).