Redox Cycling with Tellurium. Si−H Bond Activation by a Lewis Superacidic Tellurenyl Cation.

The <italic>C,N</italic>‐chelated aryltellurenyl triflate [2‐(<italic>t</italic>BuNCH)C6H4Te][OTf] (<bold>1</bold>) activates the Si−H bonds in the tertiary silanes R3SiH <italic>via</italic> umpolung of H− to H+ to give rise to the iminium salts (<italic>t</italic>BuN(H)CH)C6H4TeSiR3][OTf] (<bold>2R</bold>, R=Et, Ph (elusive) and R=Si(CH3)3 isolated; OTf=O3SCF3) comprising Te−Si bonds, which are capable of generating silyl triflates, R3SiOTf, under attack of a second equivalent of <bold>1</bold>. The unprecedented Si−H activation was utilized in main group redox catalysis using <italic>p</italic>‐quinones, which were converted into (silylated) hydroquinones. [ABSTRACT FROM AUTHOR]