Aluminum clusters, reactions with oxygen

Figure 22. Series of mass spectra showing progression of the etching reaction of aluminum anions with oxygen. Note that magic number clusters corresponding to electron shell closings for 40 and 70 electrons (AI13 and AI23) appear as the terminal product species of reactions with oxygen at flow rates of (a) 0.0, (b) 7.5, and (c) 100.0 standard cubic centimeters per minute (seem). Taken with permission from ref. 92.

Leuchner, R. E. Harms, A. C. Castleman, A. W. Thermal metal cluster anion reactions Behavior of aluminum clusters with oxygen. J. Chem. Phys. 1989,91, 2753 Aluminum cluster reactions. 1991, 94, 1093. 

Khanna et al. [136] proposed a mechanism of the reactions of aluminum based clusters with O, which lends a physical interpretation as to why the HOMO-LUMO gap of the clusters successfully predicts the oxygen etching behaviors. The importance of the HOMO-LUMO gap strongly suggests that the reactions of the metal clusters belong to the pseudoexcitation band. 

The reaction of zirconium tetrachloride and hexamethylbenzene in the presence of aluminum and aluminum trichloride at 120°C produces a melt, which upon hydrolysis with water in the presence of methylene chloride, yields an organic-soluble species of composition [Zr3(C6(CH3)8-Cle]Cl. The brown product has a magnetic moment at 303°K of 2.04 B.M. Conductivity measurements have been interpreted in terms of the trinuclear cluster cation. It decomposes in nitrogen at 20°-30°C and is rapidly oxidized by oxygen 179). 

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