Zinc Imine Polyhedral Oligomeric Silsesquioxane as a Quattro‐Site Catalyst for the Synthesis of Cyclic Carbonates from Epoxides and Low‐Pressure CO2.

In the present research, the synthesis, spectroscopic characterization, and structural investigations of a unique ZnII complex of imine‐functionalized polyhedral oligomeric silsesquioxane (POSS) is designed, and hereby described, as a catalyst for the synthesis of cyclic carbonates from epoxides and CO2. The uncommon features of the designed catalytic system is the elimination of the need for a high pressure of CO2 and the significant shortening of reaction times commonly associated with such difficult transformations like that of styrene oxide to styrene carbonate. Our studies have shown that imine‐POSS is able to chelate metal ions like ZnII to form a unique coordination complex. The silsesquioxane core and the hindrance of the side arms (their steric effect) influence the construction process of the homoleptic Zn4@POSS‐1 complex. The compound was characterized in solution by NMR (1H, 13C, 29Si), ESI‐MS, UV/Vis spectroscopy and in the solid state by thermogravimetric/differential thermal analysis (TG‐DTA), elemental analysis, diffuse reflectance infrared Fourier transform spectroscopy (DRIFTS), cross‐polarization magic angle spinning (CP MAS) NMR (13C, 29Si) spectroscopy, and X‐ray crystallography. [ABSTRACT FROM AUTHOR]