Mono- and Dinuclear Macrocyclic Calcium Complexes as Platforms for Mixed-Metal Complexes and Clusters

Mono- and dinuclear calcium complexes of the Schiff-base macrocycles H4 L have been prepared and characterized spectroscopically and crystallographically. In the formation of Ca­(THF)2­(H2 L 1 ), Ca2(THF)2­(μ-THF)­(L 1 ), and Ca2(THF)4­(L 2 ), the ligand framework adopts a bowl-shaped conformation instead of the conventional wedge, Pacman-shaped structure as seen with the anthracenyl-hinged complex Ca2(py)5(L 3 ). The mononuclear calcium complex Ca­(THF)2­(H2 L 1 ) reacts with various equivalents of LiN­(SiMe3)2 to form calcium/alkali metal clusters and dinuclear transition metal complexes when reacted subsequently with transition metal salts. The dinuclear calcium complex Ca2(THF)2­(μ-THF)­(L 1 ), when reacted with various equivalents of NaOH, is shown to act as a platform for the formation of calcium/alkali metal hydroxide clusters, displaying alternate wedged and bowl-shaped conformations.