title: Methyltriskaidecazirconates, molecular forms of zirconia.
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.
authors: Department of Chemistry, University of Nebraska, Lincoln, Nebraska 68588, USA. vday@unl.edu
authors: Victor W
authors: VW
authors: Day
authors: Walter G
authors: WG
authors: Klemperer
authors: Margaret Mary
authors: MM
authors: Pafford
mesh_terms: D018360:Crystallography, X-Ray; D006868:Hydrolysis; D009682:Magnetic Resonance Spectroscopy; D008958:Models, Molecular; D009942:Organometallic Compounds / Q000737:chemistry*; D013237:Stereoisomerism; D015040:Zirconium / Q000737:chemistry*
chemical_list: D009942:Organometallic Compounds; D015040:Zirconium; C028541:zirconium oxide