Synthesis and Modular Reactivity of Low Valent Al/Zn Heterobimetallics Supported by Common Monodentate Amides

Recent advances on low valent main group metal chemistry have shown the excellent potential of heterobimetallic complexes derived from Al(I) to promote cooperative small molecule activation processes. A signature feature of these complexes is the use of bulky chelating ligands which act as spectators providing kinetic stabilization to their highly reactive Al-M bonds. Here we report the synthesis of novel Al/Zn bimetallics prepared by the selective formal insertion of AlCp* into the Zn-N bond of the utility zinc amides ZnR2 (R=HMDS, hexamethyldisilazide; or TMP, 2,2,6,6-tetramethylpiperidide). By systematically assessing the reactivity of the new [(R)(Cp*)AlZn(R)] bimetallics towards carbodiimides, structural and mechanistic insights have been gained on their ability to undergo insertion in their Zn-Al bond. Disclosing a ligand effect, when R=TMP, an isomerization process can be induced giving [(TMP)2AlZn(Cp*)] which displays a special reactivity towards carbodiimides and carbon dioxide involving both its Al-N bonds, leaving its Al-Zn bond untouched. A simple and easy to access heterobimetallic system based on Al/Zn combinations is installed. Utilizing Cp*, HMDS and TMP ligands enables regioselective insertions of carbodiimides and ligand substitutions directly at the metal-metal bond. These transformations are accompanied by state-of-the-art quantum chemical calculations. image