Synthesis, structure and properties of two unexpected square pyramidal pentanuclear oxo-isopropoxide molecules: Ce5O(OPri)(13) and La5O(OPri)(13)(HOPri)(2)
2012 (English)In: Inorganica Chimica Acta, ISSN 0020-1693, E-ISSN 1873-3255, Vol. 384, 125-132 p.Article in journal (Refereed) Published
The synthesis, structure and properties of two pentanuclear oxo-alkoxides are described. A combination of metathesis of LnCl(3) and 3KOPr(i) and stoichiometric hydrolysis resulted in the solvated oxo-alkoxide La5O(OPri)(13)(HOPri)(2) (1) and the non-solvated Ce5O(OPri)(13) (3). 1 is rather stable at room-temperature, but desolvation into La5O(OPri)(13) (2), identified by spectroscopy, could be achieved by vacuum treatment. 1 and 3 were structurally characterised by single-crystal X-ray diffraction. In both 1 and 3 the metal atoms have a square pyramidal arrangement. In 1, each crystallographically independent La5O(OPri)(13) (HOPri)(2) molecule contains 3 six-coordinated and 2 seven-coordinated La atoms, while in 3 all Ce atoms are six-coordinated. 3 Is the first structurally characterized example of a purely Ce3+ isopropoxide. Characterisations of 1 and 3 were by IR- and Raman spectroscopy and differential scanning calorimetry, and for 1 also by H-1 and C-13 NMR spectroscopy. The great similarity of the IR spectra of the solid 1 and 3, respectively, to their corresponding solutions, showed that the molecular structure present in the solid state is close to retained in solution.
Place, publisher, year, edition, pages
2012. Vol. 384, 125-132 p.
Lanthanide, Alkoxides, Oxo-ligand, Cerium, Lanthanum, Metathesis
IdentifiersURN: urn:nbn:se:su:diva-76122DOI: 10.1016/j.ica.2011.11.041ISI: 000301179600017OAI: oai:DiVA.org:su-76122DiVA: diva2:526177