The mechanism of the reaction between MAO and TMA: DFT study of the electronic structure and characterization of transition states for [AlOMe], [AlOMe] and [AlOMe] cages.

Methylaluminoxane (MAO) and trimethylaluminium (TMA) are relevant compounds in organometallic catalysis. Despite many published studies, aspects of their interaction persist an unsolved puzzle. Hence, in this work, we used quantum mechanic approaches based on density functional theory to study this topic. Our calculations revealed that interaction between MAO and TMA occurs initially by the formation of an intermediary Lewis adduct. In agreement with the latent acidity concept, the activation energy for the tensioned Al-O bond break is small, and changes with the local environment of the MAO cages. Breakage of bond belonging to two square faces requires between 4.20 and 5.80 kcal/mol, whereas square-hexagonal faces demand 0.61-9.43 kcal/mol. The products of this reaction present a terminal, acidic 3-coordinate aluminum atom, that can be capped by another TMA molecules. However, our computations suggest that entropic effects may prevent this reaction from occurring at all these sites in the MAO models studied. Additionally, we also characterize the inter/intramolecular methane elimination mechanism. These reactions are not feasible at room temperature but may occur at high temperatures.