From Cages to Sheets: Computational Elucidation of Methylaluminoxane Structure and Reactivity

Abstract

Methylaluminoxane (MAO) is the most widely used cocatalyst in single‐site olefin polymerization, yet its molecular structures have decisively resisted characterization. Computational chemistry has played an indispensable role throughout the characterization efforts, from the earliest cage‐based structural proposals inspired by tert‐butylaluminoxane analogs through systematic hydrolysis‐based modeling to the identification of two‐dimensional sheet structures as the thermodynamically preferred motif. This review traces that computational journey, with particular attention to the methodological advances and failures that shaped it. The discovery that widely used density functional theory methods for MAO carry systematic errors for four‐coordinate aluminum–oxygen environments, and that vibrational entropy rather than electronic energy is the decisive thermodynamic quantity in the experimentally relevant size domain, fundamentally redirected the field. The resulting ovalene‐based sheet model for the dominant [(AlOMe)16(AlMe3)6Me]− anion is simultaneously consistent with electrospray ionization mass spectrometry, solid‐state NMR, X‐ray crystallography, and synchrotron pair distribution function data, and yields catalyst activation barriers in reasonable agreement with experiment. The structural foundation now established for the dominant anionic component of fresh MAO opens a realistic path toward understanding the full complexity of the MAO mixture and toward rational design of next‐generation aluminum‐based cocatalysts.