Catch & Release of Al(I) at a Zinc Bis-Amide

[(HMDS)(Cp*)Al]2Zn (1) is an intriguing trimetallic zinc aluminyl for which reactivity and quantum chemical studies remain elusive. Through a combined experimental and computational approach 1 is revisited showcasing its reversible formation and reaction chemistry. As revealed computationally, the compound is prone to eliminate and transfer monomeric [AlCp*] – reminiscent of Schnöckels (AlCp*)4. Experimental validation is provided based on NMR studies which showcase the transfer of one and two equivalents of [AlCp*] possible with suitable trapping reagents. Without trapping reagents and thermal treatment of 1, Cp* transfer, Al(HMDS) release and decomposition pathways are induced. Disclosing complementary reactivity, sequential insertion of carbodiimides into 1 yields a series of carbene complexes through one- and twofold insertions. All transformations are followed by state-of-the-art chemical calculations to understand the chemical bonding and bimetallic cooperation between the elements Al and Zn in-depth.