Synthesis and structure of dinuclear hafnium(IV) and zirconium(IV) complexes sandwiched between 2 mono-lacunary α-Keggin polyoxometalates

The synthesis and characterization of two dinuclear HfIV and ZrIV complexes sandwiched between 2 mono-lacunary alpha-Keggin polyoxometalates (POMs), i.e., (Et2NH2)8[{alpha-PW11O39Hf(micro-OH)(H2O)}2].7H2O (Et2NH(2)-1) and (Et2NH2)8[{alpha-PW11O39Zr(micro-OH)(H2O)}2].7H2O (Et2NH(2)-2), are described. [Note: the moieties of their polyoxoanions are abbreviated simply as and , respectively.] A pair of HfIV- and ZrIV-containing POMs belonging to the same family were herein isolated as diethylammonium salts and were unambiguously characterized by complete elemental analysis, including sodium and oxygen analyses, TG/DTA, FT-IR, single-crystal X-ray structure analysis and solution (31P and 183W) NMR spectroscopy. Polyoxoanions 1 and 2 were isostructural with each other. The central [M2(micro-OH)2(H2O)2]6+ (M=Hf, Zr) cation unit was composed of 2 edge-sharing polyhedral M units, which were linked through 2 micro-OH groups and contained 1 water molecule coordinated to each metal center. Since the mono-lacunary Keggin POM acts as an oxygen-donor quadridentate ligand, the Hf and Zr centers are 7-coordinate. It should be noted that the present 2 Keggin 2:2-type compounds, Et2NH(2)-1 and Et2NH(2)-2, undergo a reversible conversion to Keggin 1:2-type complexes [M(alpha-PW11O39)2]10-, respectively, in solution under appropriate conditions. The synthesis of Et2NH(2)-1 and Et2NH(2)-2 is based on such an interconversion. The Zr compound Et2NH(2)-2 was rigorously compared with the 3 Zr POMs (OK-1-OK-3), recently reported by Kholdeeva's group: their POMs in a different protonation-state did not contain any coordinating water molecules.