Unveiling Complexity of the Oxygenation of Aluminum Alkyls by the Isolation of Unique Alkylperoxide and Oxoalkoxide Compounds

[Image: see text] While aluminum alkyls are often considered to be exemplary compounds of main-group organometallics and an in-depth understanding of their multifaceted chemistry is continually vital, the controlled oxygenation of organoaluminum complexes still remains a largely undeveloped area. In the course of our systematic studies on the relationship between the Lewis acidity of metal centers and noncovalent interactions in the secondary coordination sphere, we report the oxygenation of dialkylaluminum complexes incorporating a pyrrole–ester ligand, as purposefully selected dormant Lewis acidic octet-compliant model compounds, and the isolation and characterization of a new, dimeric aluminum tert-butylperoxide and an unique example of an aluminum oxoethoxide cluster. Our studies provide a more in-depth look at the diversity and complexity of the oxygenation chemistry of aluminum alkyls.