Not Non-Coordinating at All: Coordination Compounds of the Cyclodimethylsiloxanes Dn (D = Me2SiO; n = 6, 7) and Group 2 Metal Cations

Abstract

We present the coordination chemistry of the cyclodimethylsiloxanes D6 and D7 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 Mg2+ and Ca2+ even with iodide employed as the anion and for Sr2+ and Ba2+ in the presence of GaI3.