The Ether‐Adduct of a Lewis Superacidic, Dicoordinate Aluminum Hydride Cation and the Ion Affinities of Solvent‐Adducts

Abstract

AbstractAluminum reagents are widely used as strong Lewis acids for organic transformations and catalysis. In recent years, a variety of Al‐Lewis superacids could be accessed by preparation of aluminum cations paired with weakly‐coordinating anions or by use of perfluorinated substituents at the metal. While the majority of these Al‐Lewis superacids is composed of a tricoordinate Al‐metal atom, examples for dicoordinate Al species are very scarce. In this study, we report the preparation of [(Mes*)Al(H)(OEt2)]+[Al(ORF)4]− (Mes*=2,4,6‐tBu3‐C6H2, RF=C(CF3)3) by reaction of protonated ether [H(OEt2)2]+[Al(ORF)4]− with [Mes*AlH2]2. Structural analysis supported by computed frontier orbitals and atomic charges reveals that the cation is best described as diethylether adduct of dicoordinate [(Mes*)Al(H)]+ and acts as synthon to this low‐coordinate cation. To incorporate the masking of the coordination site by the ether, the enthalpy of dissociation is included in the computed fluoride‐ and hydride ion affinities (XIA) and entropic effects are treated by defining a “free ion affinity” (fXIA), basing on the Gibbs energy change. Hereby, the Lewis acidity of free Lewis acids as well as their solvent adducts can be estimated.