Al₂₂Cl₂₀·12L (L = THF, THP):  The First Polyhedral Aluminum Chlorides

Aluminum subhalides of the type Al(22)X(20).12L (X = Cl, Br; L = THF, THP) are the only known representatives of polyhedral aluminum subhalides and exhibit interesting multicenter bonding properties. Herein, we report on the synthesis and structural investigation of the first chlorides of this type. Additional investigations applying solid-state (27)Al NMR (MAS), XPS (of Al(4)Cp(4) and Al(22)X(20).12L), and quantum chemical calculations shed more light upon the structure of the molecules and possible Al modifications.