Dihydrogen Activation by Lithium‐ and Sodium‐Aluminyls. (31st August 2021)

• Record Type: Journal Article
• Authors: Evans, Matthew J.; Anker, Mathew D.; McMullin, Claire L.; Neale, Sam E.; Coles, Martyn P.
• Is Part Of: Angewandte Chemie. Volume 133:Number 41(2021)
• Page Start: 22463
• Page End: 22466
• Publication Date: 2021-08-31
• Subjects: aluminyl anion -- dihydrogen activation -- lithium aluminyl -- sodium aluminyl; Chemistry -- Periodicals; 540
• DOI: 10.1002/ange.202108934
• Languages: English
• ISSNs: 0044-8249

Abstract

Abstract: To date, aluminyl anions have been exclusively isolated as their potassium salts. We report herein the synthesis of the lithium and sodium aluminyls, M 2 [Al(NON Dipp )]2 (M =Li, Na. NON Dipp =[O(SiMe2 NDipp)2 ] 2− ; Dipp=2, 6‐ i Pr2 C6 H3 ). Both compounds crystallize from non‐coordinating solvent as "slipped" contacted dimeric pairs with strong M ⋅⋅⋅π(aryl) interactions. Isolation from Et2 O solution affords the monomeric ion pairs (NON Dipp )Al‐M (Et2 O)2, which contain discrete Al−Li and Al−Na bonds. The ability of the full series of Li, Na and K aluminyls to activate dihydrogen is reported. Abstract : It turns out there is nothing special about potassium after all: Sodium and lithium metal reduce Al III iodide precursors to the M 2 [Al(NON Dipp )]2 aluminyls (M =Li, Na). Addition of Et2 O afforded the monomeric ion pairs (NON Dipp )Al‐M (Et2 O)2 containing unsupported Al−Li and Al−Na bonds. All species activate dihydrogen, albeit at significantly different rates of reaction.