Oxide formation upon thermolysis of a Pb(II)/Zr(IV) alkoxide
- Indiana Univ., Bloomington, IN (United States)
While Pb({mu}-O{sup t}Bu){sub 3}Zr(O{sup t}Bu){sub 3} is stable for days in refluxing toluene, addition of stoichiometric [Pb(O{sup t}Bu){sub 2}]{sub 3} prior to reflux yields {sup t}BuOH, H{sub 2}C=CMe{sub 2}, and Pb{sub 3}ZrO(O{sup t}Bu){sub 8}, which was characterized by multinuclear NMR and X-ray diffraction. Highly pure [Pb(O{sup t}Bu){sub 2}]{sub 3} itself is unchanged in refluxing toluene, although it is slowly converted to Pb{sub 4}O(O{sup t}Bu){sub 6} by catalytic quantities of {sup t}BuOH, LiNme{sub 2}, or HN(SiMe{sub 3}){sub 2}, but not by Pb metal. Stoichiometric water converts [Pb(O{sup t}Bu){sub 2}]{sub 3} completely to Pb{sub 4}O(O{sup t}Bu){sub 6}, which reacts at 25{degree}C with Zr(O{sup t}Bu){sub 4} to give Pb{sub 3}ZrO(O{sup t}Bu){sub 8}. The mechanism of the formation of Pb{sub 3}ZrO(O{sup t}Bu){sub 8} is suggested to involve O/C heterolysis and C-H bond scission as the rate determining step during thermolysis. Convenient syntheses of Pb{sub 4}O(O{sup t}Bu){sub 6} and Pb{sub 6}O{sub 4}(O{sup t}Bu){sub 4} are described, and {sup 207}Pb and {sup 17}O NMR spectra of all species are described. Crystallographic data for Pb{sub 3}ZrO(O{sup t}Bu){sub 8} (at -174{degree}C) include a = 16.663(2) A, b = 12.608(1), c = 21.117(2), and Z = 4 in space group Pbc2{sub 1}. 27 refs., 2 figs., 2 tabs.
- OSTI ID:
- 249681
- Journal Information:
- Journal of the American Chemical Society, Vol. 118, Issue 17; Other Information: PBD: 1 May 1996
- Country of Publication:
- United States
- Language:
- English
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