Interaction of Carbon Dioxide with Transition-Metal-Substituted Heteropolyanions in Nonpolar Solvents. Spectroscopic Evidence for Complex Formation.

Tetraheptylammonium salts of various transition-metal-substituted heteropolyanions with alpha-Keggin ([XW(11)O(39)M](n)()(-)), alpha-Wells-Dawson ([P(2)W(17)O(61)M](m)(-)), and Weakley and Finke structures ([P(2)W(18)O(68)Co(4)](10)(-)) were investigated with respect to their reactivity with CO(2) in nonpolar solvents. It was found that copper(II)- and manganese(III)-substituted heteropolyanions do not react with CO(2). Germano- and silicotungstates with the alpha-Keggin structure do form complexes with CO(2) when substituted with Co(II), Ni(II), and Mn(II).