Isolation of new polynuclear aluminium amides; trinuclear [AlCl(MeNCH2CH2NMe)(2)(Al(NMe2)Cl)(Al(NMe2)(2))] and fluxional adamantane-like [Al4Cl2(NMe2)(6)(NMe)O]

In attempted transamination reactions involving [Al-2(NMe2)(6)] and the ami nes, N,N'-dimethylethylenediamine, DMEDA, or diethylenetriamine, DETA, inso luble white powders were formed. Two unexpected compounds, trinuclear [AlCl (MeN-CH2CH2NMe)(2)(Al(NMe2)Cl)(Al(NMe2)(2))] (1) and adamantane-like [Al4Cl 2(NMe2)(6)(NMe2)(6)(NMe)O] 2) were isolated in similar reactions where the aluminium amide sample [Al-2(NMe3)(6)] contained some 1% residual chloride. Compound 2 was also identified (by NMR and mass spectroscopy) as the major product from the reaction between Al2Cl6 and LiNMe2 (1:5) in the presence of traces of water. The compounds 1 and 2 have been characterized by X-ray crystallography, mass spectroscopy and NMR. Variable temperature solution p hase proton NMR shows that there is inversion at nitrogen in the bridging a mides in adamantanoid structure 2. (C) 2000 Elsevier Science S.A. All right s reserved.