Incorporating trimethylaluminium into the structures of alkali metal (Li, Na, K, Cs) dihydropyridines

Mulvey, Robert E. and Doherty, Shay P. and Banerjee, Sumanta and Clegg, William and Palin, Fiona J. and Kennedy, Alan R. and Robertson, Stuart D. (2022) Incorporating trimethylaluminium into the structures of alkali metal (Li, Na, K, Cs) dihydropyridines. Zeitschrift fur Anorganische und Allgemeine Chemie, 649 (5). ISSN 0044-2313 (https://doi.org/10.1002/zaac.202200356)

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Abstract

AbstractCo‐complexation of equimolar amounts of 1‐alkali‐metal‐2‐tertbutyldihydropyridines with AlMe3 in the presence of a polydentate N‐donor ligand has delivered four crystallographically verified alkali‐metal aluminates [donor⋅AM(μ‐tBuDHP)AlMe3]n (1, AM=Li, donor=TMEDA, n=1; 2, AM=Na, donor=PMDETA, n=1; 3, AM=K, donor=PMDETA, n=2; 4, AM=Cs, donor=PMDETA, n=∞; TMEDA=N,N,N′,N′‐tetramethylethylenediamine; PMDETA=N,N,N′,N′′,N′′‐pentamethyldiethylenetriamine). While the monomeric complexes (1, 2) and the polymeric complex (4) are thermally stable, the dimeric complex (3) undergoes a disproportionation process yielding the known ion‐separated homoanionic complex [K ⋅ (PMDETA)2]+ [AlMe4]− (3 a). Utilizing TMEDA as the N‐donor resulted in the same disproportionation, but gave rise to two distinct solid‐state aggregated forms of aluminate [K ⋅ (TMEDA)2]+ [AlMe4]−, namely monomeric (3 b) and polymeric (3 b′) polymorphs, in which the anionic moiety acts as a bidentate chelator or monodentate bridge respectively to the potassium cationic moieties.

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