Evans-Showell-type polyoxometalate constructing novel 3D inorganic architectures with alkaline earth metal linkers: syntheses, structures and catalytic properties.

Four new architectures containing [CoMoHO] polyoxoanions, (CNH)[Sr(HO)][CoMoHO]·2HO 1, (CNH)[Ba(HO)][CoMoHO]·3HO 2, (CNH)[Sr(HO)][CoMoHO]·3HO 3 and (CNH)[Ba(HO)][Ba(HO)][CoMoHO]·2HO 4 (CNH = ethylenediamine; CNH = 1,3-propanediamine) have been synthesized and characterized by elemental analysis, IR spectroscopy, solid diffuse reflective spectroscopy, TG analysis, powder X-ray diffraction and single crystal X-ray diffraction. Compounds 1 and 2 obtained in the presence of ethylenediamine, are made of Evans-Showell-type anions [CoMoHO], linked by Sr or Ba cations to form 3D frameworks. To our knowledge, compound 1(2) represents the first example of 3D architecture in which the Evans-Showell anions [CoMoHO] were linked by pure alkaline earth cations. When propanediamine was used instead of ethylenediamine, compounds 3 and 4 with 2D networks were obtained. This phenomenon indicates that the organic cations, which adjust the reaction pH values, can induce different dimensional inorganic frameworks. As heterogeneous catalysts, compounds 1-4 show excellent catalytic performance in the cyanosilylation of carbonyl compounds. Furthermore, these catalytic reactions were performed under solvent-free conditions using only a low amount of the catalysts, and these catalysts can be recovered and reused without displaying any significant loss of activity. As far as we know, compounds 1-4 represent the first examples of cyanosilylation catalyzed by POM-based species containing alkaline earth metal cations.