Alkaline Earth Cluster Compounds AE[W6I14] and the Solvate [Ca(C2H6SO)6][W6I14]

Alkaline earth tungsten iodide clusters AEW₆I₁₄] with AE = Mg, Ca, Sr, Ba and the solvated compound Ca(C₂H₆SO)₆]W₆I₁₄] were prepared and structurally characterized. A new synthesis was employed, starting from W₆I₂₂, which is an exceptional compound among binary tungsten iodides because it is soluble in common polar organic solvents. As evidence for the wide range of the applicability of W₆I₂₂, we report the synthesis of the new AEW₆I₁₄] compounds in comparison to a solid‐state reaction departing from W₃I₁₂.