The C,N-chelated aryltellurenyl triflate [2-(tBuNCH)CHTe][OTf] (1) activates the Si-H bonds in the tertiary silanes RSiH via umpolung of H to H to give rise to the iminium salts (tBuN(H)CH)CHTeSiR][OTf] (2, R=Et, Ph (elusive) and R=Si(CH) isolated; OTf=OSCF) comprising Te-Si bonds, which are capable of generating silyl triflates, RSiOTf, under attack of a second equivalent of 1. The unprecedented Si-H activation was utilized in main group redox catalysis using p-quinones, which were converted into (silylated) hydroquinones.
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