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Incorporating Trimethylaluminium into the Structures of Alkali Metal (Li, Na, K, Cs)dihydropyridines

Lookup NU author(s): Emeritus Professor Bill CleggORCiD



This is the authors' accepted manuscript of an article that has been published in its final definitive form by Wiley-VCH Verlag GmbH & Co. KGaA, 2022.

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Co-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(m-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 = Ꚙ; 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]¯ (3a). 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 (3b) and polymeric (3b’) polymorphs, in which the anionic moiety acts as a bidentate chelator or monodentate bridge respectively to the potassium cationic moieties.

Publication metadata

Author(s): Mulvey RE, Docherty SP, Banerjee S, Clegg W, Palin FJ, Kennedy AR, Robertson SD

Publication type: Article

Publication status: Published

Journal: Zeitschrift fuer anorganische und allgemeine Chemie

Year: 2022

Online publication date: 09/12/2022

Acceptance date: 08/12/2022

Date deposited: 15/12/2022

ISSN (print): 0044-2313

ISSN (electronic): 1521-3749

Publisher: Wiley-VCH Verlag GmbH & Co. KGaA


DOI: 10.1002/zaac.202200356

ePrints DOI: 10.57711/z5cd-v315


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Funder referenceFunder name
Leverhulme Trust