A New Structural Motif in Aggregation of Methylalumoxanes: Non‐Hydrolytic Route by the Alkylation of Dicarboxylic Acids.

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, [([(O2CCH2C6H4CO2)(μ‐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. [ABSTRACT FROM AUTHOR]