| Autor: |
Gaunt, Andrew J., May, Iain, Sarsfield, Mark J., Collison, David, Helliwell, Madeleine, Denniss, Iain S. |
| Zdroj: |
Dalton Transactions; 2003, Vol. 2003 Issue: 13 p2767-2771, 5p |
| Abstrakt: |
The syntheses and the crystal structures of NH411LnIIIPMo11O392·16H2O LnIII Ce 1, Sm 2, Dy 3 or Lu 4 are reported in which an LnIIIcation is sandwiched between two ‘lacunary’ PMo11O397−anions to give a complex with eight oxygen atoms coordinated to the lanthanide centre in a twisted square antiprismatic geometry. This analogous series of complexes represents only the second time that the PMo11O397−anion has been fully crystallographically characterised. All four compounds are synthesised in high yield and characterised by a range of physical and spectroscopic techniques. 31P NMR, Raman and UVVisnIR spectroscopies give a clear indication that the LnIIIPMo11O39211−anion is also stable in solution. As LnIIIcontracts across the lanthanide series the Ln–O bond distances decrease and the splitting of the νP–Ovibrational mode within the PMo11O397−unit increases. The relative stability of this species in solution may have importance in elucidating the speciation of Lniii and Aniii cations in nuclear waste solutions where phosphopolymolybdate anions are known to form. |
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