While Pb(mu-O(t)Bu)(3)Zr(O(t)Bu)(3) is stable for days in refluxing toluene, addition of stoichiometric [Pb(O(t)Bu)(2)](3) prior to reflux yields (t)BuOH, H2C=CMe(2), and Pb3ZrO(O(t)Bu)(8), which was characterized by multinuclear NMR and X-ray diffraction. Highly pure [Pb(O(t)Bu)(2)](3) itself is unchanged in refluxing toluene, although it is slowly converted to Pb4O(O(t)Bu)(6) by catalytic quantities of (t)BuOH, LiNMe(2), or HN(SiMe(3))(2), but not by Pb metal. Stoichiometric water converts [Pb(O(t)Bu)(2)]3 completely to Pb4O(O(t)Bu)(6), which reacts at 25 degrees C with Zr(O(t)Bu)(4) to give Pb3ZrO-(O(t)Bu)(8). Since PbZr(O(t)Bu)(6) and [Pb(O(t)Bu)(2)](3) show no NMR spectroscopic evidence of reacting at 25 degrees C in toluene, the mechanism of the formation of Pb3ZrO(O(t)Bu)(8) is suggested to involve O/C heterolysis and C-H bond scission as the rate determining step during thermolysis. Convenient syntheses of Pb4O(O(t)Bu)(6) and Pb6O4(O(t)Bu)(4) are described, and Pb-207 and O-17 NMR spectra of all species are described. Crystallographic data for Pb3ZrO(O(t)Bu)(8) (at -174 degrees C)include a = 16.653(2) Angstrom, b = 12.608(1), c = 21.117(2), and Z = 4 in space group Pbc2(1).