Confirmation of the Semivacant Wells−Dawson Polyoxotungstate Skeleton. The Structures of [Ce{X(H4)W17O61}2]19- (X = P, As) Indicate the Probable Location of Internal Protons
- 21 December 2004
- journal article
- research article
- Published by American Chemical Society (ACS) in Inorganic Chemistry
- Vol. 44 (2) , 169-171
Abstract
Reaction of Ce(III) with lacunary versions of [H4XW18O62]7- (X = P, As) yields the 1:2 complexes [Ce(H4XW17O61]19- (X = As, 1; P, 2) in good yield, characterized in solution and the solid state by NMR spectroscopy and X-ray crystallographic analysis, respectively. The structures confirm a syn C2 conformation that is analogous to that observed for [Ln(α2-P2W17O61)2]17- but with “empty” O4 tetrahedra that are in positions remote from the cerium atom. Bond valence sum calculations for these structures show that the four protons that are required for charge balance in all salts of the XW18 anions and their lacunary derivatives are almost certainly bound to the oxygen atoms of the empty tetrahedra.Keywords
This publication has 9 references indexed in Scilit:
- Multiple Diastereomers of [M n+(α m -P2W17O61)2](20−n)− (M=UIV, ThIV, CeIII; m=1, 2). Syn- and Anti-Conformations of the Polytungstate Ligands in α1α1, α1α2, and α2α2 ComplexesJournal of Cluster Science, 2003
- Polyoxometalates: Reactivity2003
- Formation of voltammetrically-active isopolyoxotungstate complexes in aqueous CH3CN mediaInorganica Chimica Acta, 2000
- Keggin Cluster Formation by Hydrothermal Reaction of Tungsten Trioxide with Methyl Substituted Ammonium: The Crystal Structure of Two Novel Compounds, [NH2(CH3)2]6H2W12O40· ∼4H2O and [N(CH3)4]6H2W12O40· 2H2OJournal of Solid State Chemistry, 1996
- Reformulation of the hexafluorooctadecatungstate anion as a heteropoly sodate complex: [H2F6NaW18O56]7-Inorganic Chemistry, 1990
- Bond-valence parameters obtained from a systematic analysis of the Inorganic Crystal Structure DatabaseActa crystallographica Section B, Structural science, crystal engineering and materials, 1985
- New chemistry for heteropolyanions in anhydrous nonpolar solvents. Coordinative unsaturation of surface atoms. Polyanion oxygen carriersJournal of the American Chemical Society, 1984
- Location of internal hydrogen atoms in the paradodecatungstate polyanion by neutron diffractionJournal of the American Chemical Society, 1983
- High resolution PMR of several isopolytungstates and related compoundsJournal of Inorganic and Nuclear Chemistry, 1976