Supramolecular Chemistry Based on Gallium–Gallium Single Bonds – Formation of Large Heterocycles and Cages with up to Twelve Gallium Atoms

The tetraalkyldigallium(II) compound R2Ga–GaR2 (1) [R = CH(SiMe3)2] reacted with amino and hydroxo functionalized carboxylic acids by retention of the Ga–Ga bond and release of CH2(SiMe3)2. New heterocyclic or cage-like compounds were formed with three, two, or six Ga–Ga bonds in a single molecule. The latter dodecagallium compounds encapsulated THF or dioxane molecules in their molecular cavities (carcerands), the other compounds have up to six THF molecules coordinated by N–H···O hydrogen bonds.