The interaction of dioxygen with various tetrahedral aluminum alkyls, (tBu)3Al.OEt2 (1), tBu2Al(mu-OtBu)2AltBu2 (6), (tBu)2Al(mesal) (2) [mesal=methyl salicylate anion], R2Al(mu-pz)2AlR2 [pz=deprotonated pyrazole, R= Me (3a), Et (3b), and tBu (3c)], R2Al(mu-3,5-Me2pz)2AIR2[3,5-Me2pz = deprotonated 3,5-dimethylpyrazole, R= Me (4a), and Et (4b)], and Et2B(mu-pz)2AlEt2 (5), has been investigated. We were particularly interested in the effect of steric hindrances both caused by the metal-bonded substituents and those that result from the nature of the bifunctional ligand used in the oxygenation reaction. In the reaction of 1 with O2, only the formation of the monoalkoxide compound6 was observed. The latter di-tert-butyl compound as well as all planar aluminapyrazoles, that is, the tert-butyl derivative 3c and lower alkylaluminum derivatives with the more demanding 3,5-dimethylpyrazoyl ligands 4a and 4b, are stable under an atmosphere of dry oxygen and ambient conditions. Inspection of the space-filling representation of these compounds has undoubtedly shown that the bulky tert-butyl groups or pyrazolyles ligands, respectively, provide steric protection for the metal center from the dioxygen attack. In contrast, the dialkylaluminum derivatives of pyrazole, 3a and 3b, and the diethylaluminum bis(1-pyrazolyl)borate complex 5, all with the metal center eclipsed with respect to the plane defined by the four nitrogen atoms, react smoothly with O2 to form the alkyl(alkoxy)aluminum complexes. In the reaction of 5 with O2 for example, the Et-B bonds remained intact, and the dimeric five-coordinate compound [Et2B(mu-pz)2 Al(mu-OEt)Et]2 (9) was isolated in good yield. The interaction of mononuclear di-tert-butyl chelate complex 2 with O2 at -15 degrees C gives (tBuOO)(tBuO)Al(mu-OtBu)2Al(mesal)2 (7) in high yield, and the presence of the alkylperoxo moiety is a particularly significant point in the resulting product. All the compounds have been characterized spectroscopically, and the structures of 3c, 4a, 6, 7, and 9 have been confirmed by X-ray crystallography. Structural features of 1-6 are discussed and are considered in relation to the possible approach pathways of the O2 molecule to the four-coordinate metal center. This analysis and the observed apparent dissimilarity in the reactions of model four-coordinate aluminum alkyls with O2 clearly show that the stereoelectronic prerequisites are responsible for the fundamentally different reactivity.

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Metal–organic frameworks (MOFs) have attracted a great deal of attention in the areas of biomedicine due to their versatile porous structures and are potentially ideal vehicles for loading bioactive molecules and controlling the release of small molecules. Current approaches for encapsulation of drug molecules in MOFs are usually based on multistep wet processes. We report here a novel simple and rapid solid‐state process that combines the mechanosynthesis of HKUST‐1 and the encapsulation of ibuprofen (IBU‐H), as a model drug molecule, in a one‐pot reaction involving a pre‐assembled [Cu2(IBU)4]·2DMF cluster. The ibuprofen‐loaded MOF composite (with 58.5 wt.‐% loading capacity) was also studied as a drug delivery carrier system in phosphate buffered saline (PBS) solution at 37 °C.

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