Silicon Tetrakis(trifluoromethanesulfonate): A Simple Neutral Silane Acting as a Soft and Hard Lewis Superacid

A facile synthesis and isolation of pristine silicon tetrakis(trifluoromethanesulfonate), Si(OTf)(4), is reported, acting as the first neutral silicon‐based Lewis superacid suitable towards soft and hard Lewis bases. Its OTf groups have a dual function: they are excellent leaving groups and modulate the degree of reactivity towards soft and hard Lewis bases. Exposed to soft Lewis donors, Si(OTf)(4) leads to [L(2)Si(OTf)(4)] complexes (L=isocyanide, thioether and carbonyl compounds) with retention of all Si−OTf bonds. In contrast, it can cleave C−X bonds (X=F, Cl) of hard organic Lewis bases with a high tendency to form SiX(4) (X=F, Cl) after halide/triflate exchange. Most notable, Si(OTf)(4) allows a gentle oxydefluorination of mono‐ and bis(trifluoromethyl)benzenes, resulting in the formation of the corresponding benzoylium species, which are stabilized by the weakly coordinating [Si(OTf)(6)] dianion.