The ether‐adduct of a lewis superacidic, dicoordinate aluminum hydride cation and the ion affinities of solvent‐adducts
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
- Standort
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Deutsche Nationalbibliothek Frankfurt am Main
- Umfang
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Online-Ressource
- Sprache
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Englisch
- Anmerkungen
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Zeitschrift für anorganische und allgemeine Chemie. - 650, 21 (2024) , e202400099, ISSN: 1521-3749
- Ereignis
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Veröffentlichung
- (wo)
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Freiburg
- (wer)
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Universität
- (wann)
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2024
- Urheber
- DOI
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10.1002/zaac.202400099
- URN
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urn:nbn:de:bsz:25-freidok-2558496
- Rechteinformation
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Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
- Letzte Aktualisierung
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15.08.2025, 07:33 MESZ
Datenpartner
Deutsche Nationalbibliothek. Bei Fragen zum Objekt wenden Sie sich bitte an den Datenpartner.
Beteiligte
- Dabringhaus, Philipp
- Krossing, Ingo
- Universität
Entstanden
- 2024
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