Lessons from recent theoretical treatments of Al-M bonds (M = Fe, Cu, Ag, Au) that capture CO 2 .

Complexes with Al-M bonds (M = transition metal) have emerged as platforms for discovering new reaction chemistry either through cooperative bond activation behaviour of the heterobinuclear unit or by modifying the properties of the M site through its interaction with the Al centre. Therefore, elucidating the nature of Al-M bonding is critical to advancing this research area and typically involves careful theoretical modelling. This Frontier article reviews selected recent case studies that included theoretical treatments of Al-M bonds, specifically highlighting complexes capable of cooperative CO 2 activation and focusing on extracting lessons particular to the Al-M sub-field that will inform future studies with theoretical/computational components.