Alumoxanes are typically produced via controlled hydrolysis of short‐chain alkyl aluminium compounds which leads to oligomeric species that are usually difficult to obtain in crystalline form. Simultaneously, various alternative non‐hydrolytic approaches to alumoxanes have also been used. In this work, we report on a new methylalumoxane scaffold derived from the alkylation of a series of dicarboxylic acids: itaconic acid (HO2CCH2C(=CH2)CO2H), succinic acid (HO2CCH2CH2CO2H) and homophthalic acid (HO2CCH2C6H4CO2H). The reactions of AlMe3 with a selected dicarboxylic acid in the molar ratio 4:1 conducted at elevated temperature occur with double methylation of each carboxylic group and provide to the formation of a new methylalumoxane aggregate, Me10Al6O4, flanked by methylaluminium diolate units. We also aimed to obtain dialkylaluminium derivatives of dicarboxylic acids by the controlled reaction of the appropriate acid with AlMe3 in the 1:2 stoichiometry. While the synthesis of organoaluminium derivatives of flexible aliphatic dicarboxylic acids (itaconic and succinic acids) is challenging due to their insolubility, the related homophtalate compound readily forms a molecular tetranuclear cluster, [(homophtalate)(AlMe2)2]2. The molecular and crystal structures of the resulting compounds were determined via NMR spectroscopic analysis and single crystal X‐ray diffraction crystallography.

中文翻译：

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甲基铝氧烷聚集的新结构基序：二羧酸烷基化的非水解路线


铝氧烷通常是通过短链烷基铝化合物的受控水解来生产的，这会产生通常难以以结晶形式获得的低聚物。同时，还使用了各种替代的铝氧烷非水解方法。在这项工作中，我们报道了一种新的甲基铝氧烷支架，该支架源自一系列二羧酸的烷基化：衣康酸（HO2CCH2C(=CH2)CO2H）、琥珀酸（HO2CCH2CH2CO2H）和高邻苯二甲酸（HO2CCH2C6H4CO2H）。 AlMe3 与选定的二羧酸以 4:1 的摩尔比在高温下进行反应，每个羧基发生双甲基化，并形成新的甲基铝氧烷聚集体 Me10Al6O4，其侧翼为二醇甲基铝单元。我们还旨在通过适当的酸与 AlMe3 以 1:2 化学计量进行受控反应来获得二羧酸的二烷基铝衍生物。虽然柔性脂肪二羧酸（衣康酸和琥珀酸）的有机铝衍生物的合成由于其不溶性而具有挑战性，但相关的同邻苯二甲酸盐化合物很容易形成分子四核簇，[(同邻苯二甲酸盐)(AlMe2)2]2。通过核磁共振波谱分析和单晶 X 射线衍射晶体学确定了所得化合物的分子和晶体结构。