Taming the Lewis Superacid Al(ORF)3 (RF=C(CF3)3): DFT Guided Identification of the “Stable yet Reactive” Adduct SiPr2→Al(ORF)3; Its Use as ORF‐ Abstractor from a “Ni‐ORF” complex

A DFT study of several L→Al(ORF)3 (L=Lewis bases) adducts allowed the identification of (iPr2S)→Al(ORF)3 1‐SiPr2 as a “stable yet reactive” adduct. 1‐SiPr2 was shown to act as a masked Lewis superacid able to release Al(ORF)3 under mild conditions. It could be used to a ORF− ligand from (bipyMe2)Ni(ORF)2 (bipyMe2 : 6,6’‐dimethyl‐2,2’‐dipyridyl) and generate the nickel alkoxide complex [(bipyMe2)Ni(ORF)(iPr2S)]+[(RFO)3Al−F−Al(ORF)3]− 5. Ligand exchange of iPr2S by Ph3P yielded [(bipyMe2)Ni(ORF)(PPh3)]+[(RFO)3Al−F−Al(ORF)3]− 6. A predictive DFT study of L→Al(ORF)3 (L=Lewis bases) adducts allowed the identification of (iPr2S)→Al(ORF)3 as a “stable yet reactive” adduct, able to act as a masked Lewis superacid. It provides a novel strategy to use M‐ORF/L→Al(ORF)3 couples to generate catalytically active M+ centers featuring weakly coordinating aluminate counter anion.