Coordination of Carbon Dioxide to the Lewis Acid Site of a Zinc‐Substituted Polyoxometalate and Formation of an Adduct Using a Polyoxometalate–2,4,6‐Trimethylpyridine Frustrated Lewis Pair

Abstract

The coordination of CO2 to Lewis bases is well‐known; however, its binding to Lewis acids is much less common. The ligation of CO2 to a zinc‐substituted Wells–Dawson type polyoxometalate yielded [(n‐C8H17)4N]8[α2‐P2W17O61Zn(CO2)], which was studied by variable temperature 1H NMR, 13C NMR, and 31P NMR spectroscopy from room temperature to 201 K. The spectra were analyzed in consideration of predicted “end‐on” coordination, POM‐Zn‐O‐C‐O, and “side‐on” coordination where in addition an adjacent basic oxygen atom in the polyoxometalate binds the carbon atom of CO2. After adding 2,4,6‐trimethypyridine into the solution, a plausible adduct, POM‐CO2‐2,4,6‐trimethypyridine, was observed.