Methyltriskaidecazirconates, molecular forms of zirconia |
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Authors: | Day Victor W Klemperer Walter G Pafford Margaret Mary |
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Institution: | Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588, USA. vday@unl.edu |
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Abstract: | Repeated methanolysis of Zr(3)O](OPr(n)(10) followed by extraction and crystallization from toluene yields material that is X-ray crystallographically indistinguishable from the compound previously formulated as Zr(13)O(8)](OMe)(36). Elemental analysis and (1)H solution NMR spectroscopy strongly suggest that this material is a mixture of methyltriskaidecazirconates (MTZ) Zr(13)O(8)](OMe)(x)(OH)(36)(-)(x), x(av) approximately 20, that readily cocrystallize from hydrocarbon solution. These species have the metal-oxygen framework structure reported for Zr(13)O(8)](OMe)(36), where the 13 zirconium and 32 bridging oxygen atoms comprise a fragment of the fluorite structure adopted by ZrO(2) at elevated temperatures. Ethanolysis of Zr(3)O](OPr(n)(10) yields its ethyl analogue, Zr(3)O](OEt)(10). Both trizirconates display temperature-dependent (1)H solution NMR spectra that are interpreted mechanistically in terms of rearrangement mechanisms involving trigonal twists at the octahedral zirconium centers. |
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