A Janus‐Headed Lewis Superacid: Simple Access to, and First Application of Me3Si‐F‐Al(ORF)3

Upon reaction of gaseous Me3SiF with the in situ prepared Lewis acid Al(OR(F))3, the stable ion-like silylium compound Me3 Si-F-Al(OR(F))3 1 forms. The Janus-headed 1 is a readily available smart Lewis acid that differentiates between hard and soft nucleophiles, but also polymerizes isobutene effectively. Thus, in reactions of 1 with soft nucleophiles (Nu), such as phosphanes, the silylium side interacts in an orbital-controlled manner, with formation of Me3Si-Nu(+) and the weakly coordinating F-Al(OR(F))3(-) or ((F)RO)3Al-F-Al(OR(F))3(-) anions. If exchanged for hard nucleophiles, such as primary alcohols, the aluminum side reacts in a charge-controlled manner, with release of FSiMe3 gas and formation of the adduct R(H)O-Al(OR(F))3. Compound 1 very effectively initiates polymerization of 8 to 21 mL of liquid C4 H8 in 50 mL of CH2 Cl2 already at temperatures between -57 and -30 °C with initiator loads as low as 10 mg in a few seconds with 100% yield but broad polydispersities.