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An efficient method for the benzenium‐ion‐mediated cleavage of inert Si−C(sp3) bonds is reported. Various tetraalkylsilanes can thus be converted into the corresponding counteranion‐stabilized silylium ions. The reaction is chemoselective in the case of hexamethyldisilane. Computations reveal a mechanism with backside attack of the proton at one of the alkyl groups. Several activated Si−C(spn) bonds...
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