Experimental realisation of elusive multiple-bonded aluminium compounds : a new horizon in the aluminium chemistry

The synthesis and isolation of stable main group compounds featuring multiple bonds has been of great interest for several decades. A plethora of such multiply bonded complexes have been obtained by using sterically demanding substituents that provide both kinetic and thermodynamic stability. Most of these compounds have unusual structural and electronic properties that challenge the classical concept of covalent multiple bonding. In contrast, analogous aluminium compounds are scarce in spite of its high natural abundance. The parent dialumene (Al2H2) has been calculated to be extremely unstable, thus making compounds containing Al multiple bonds a challenging synthetic target. This Review provides an overview of the recent advances in the cutting edge synthetic approaches and the careful ligand design used to obtain aluminium homo‐ and heterodiatomic multiply bonded complexes. In addition, the reactivity of these novel compounds towards various small molecules and reagents will be discussed herein