Not Non-Coordinating at All: Coordination Compounds of the Cyclodimethylsiloxanes D (D = MeSiO; = 6, 7) and Group 2 Metal Cations.

We present the coordination chemistry of the cyclodimethylsiloxanes D and D toward alkaline earth metal salts. The coordination chemistry of these macrocycles toward alkaline earth metals has been unprecedented to date, and we could show that these ligands coordinate better than previously thought. Direct reaction of alkaline earth metal salts with these ligands yields stable complexes even with a relatively strongly coordinating iodide anion. A handful of counterintuitive coordination compounds could be characterized by single-crystal X-ray diffraction analysis. Quantum chemical calculations of suited Born-Haber cycles showed that these complexes are indeed stable, for Mg and Ca even with iodide employed as the anion and for Sr and Ba in the presence of GaI.