The Chemistry of Aluminum–Element Multiple Bonds: Synthesis, Bonding, and Reactivity

Aluminum–element multiple bonds represent a rapidly expanding frontier in main‐group chemistry, expanding the scope of aluminum from its conventional role as a highly electropositive, single‐bonded element. Through the development of sterically demanding and electronically tailored ligands, a variety of species bearing Al–B, Al–Al, Al–C, Al–N, and heavier Al–E (E = Si, P, As, and chalcogens) bonds have been successfully isolated and characterized. These compounds display diverse bonding patterns, ranging from highly polarized covalent linkages to delocalized multicenter frameworks, as elucidated by crystallographic, spectroscopic, and computational analyses. Their reactivity often departs from classical aluminum chemistry, characterized by ambiphilic behavior that enables transformations including small‐molecule activation and novel bond‐forming reactions. This review summarizes recent synthetic strategies, structural and bonding analyses, and the distinctive reactivity patterns of aluminum–element multiple bonds, and discusses the correlations between electronic structure and chemical behaviors. Continued advances in this area are expected to broaden the accessible chemical space and open pathways to functional molecular systems with potential applications in catalysis, materials development, and beyond.