The ether‐adduct of a lewis superacidic, dicoordinate aluminum hydride cation and the ion affinities of solvent‐adducts

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Abstract: Aluminum 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

Location: Deutsche Nationalbibliothek Frankfurt am Main

Extent: Online-Ressource

Language: Englisch

Notes: Zeitschrift für anorganische und allgemeine Chemie. - 650, 21 (2024) , e202400099, ISSN: 1521-3749

Event: Veröffentlichung

(where): Freiburg

(who): Universität

(when): 2024

Creator: Dabringhaus, Philipp
Krossing, Ingo

DOI: 10.1002/zaac.202400099

URN: urn:nbn:de:bsz:25-freidok-2558496

Rights: Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.

Last update: 15.08.2025, 7:33 AM CEST

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Time of origin

2024

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