Mass Spectrometry of Organometallics.II.[Diethyl Aluminum(III)Chloride-Water]System and Aluminum (III)Chloride

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Abstract
The less volatile components of the[diethyl aluminum(III)chloride?water(20: 1)]system were deduced from mass spectrometry. Ions which bear two aluminum atoms were classified to one of the proposed skeletal structures on the basis of several established facts: (1)aluminum atoms hardly change their valence during fragmentations, (2)the stability of bridge bondings increases in the order ethyl<chlorine<oxygen, and(3)even-electron ions are far more abundant than odd-electron ions. Then, the ions which bear two oxygen atoms were classified to the clusters bridged by two oxygen atoms, and the ions which bear only one oxygen atom to the clusters bridged by both oxygen and chlorine atoms. Since the transformation of an electron-deficient oxygen-bridge into a normal oxygen bond did not occur appreciably during fragmentations, the presence of ions of a certain skeletal structure could be taken as a reflect of the presence of species of the same skeletal structure in the mixed components of the sample. Cyclic sixmembered skeletal structures were proposed for ions which bear Al3O3. The mass spectrum of aluminum(III)chloride has confirmed the assumption: oxygen-bridged clusters are far more stable than chlorine-bridged clusters.

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