The disodium alkoxide of 2,6-bis(trifluoromethyl)-2,6-dihydroxy-3,3,4,4,5, 5-hexafluorooxane, C7F12O3Na2, 1, was prepared by reaction of the corresponding diol with MeONa in MeOH. This cyclic alkoxide readily mimics the reaction chemistry of the lithium and sodium alkoxides of perfluoropinacol, The reaction of the alkoxide 1 with covalent dichlorides and metallocene dichlorides yields a series of novel bicyclic ring systems. The crystal structure of the trioxasilane, 3, formed from (CH3)(2)SiCl2 was determined to provide structural information about these ring systems. Crystal data : C9H6O3F12Si, fw = 418.21 u, orthorhombic space group, Pnma (No. 62), a = 15.822(3) Angstrom, b = 12.163(3) Angstrom, c = 7.373(2) Angstrom, V = 1418.9(4) Angstrom(3), and D-calc = 1.96 g cm(-3) for Z = 4 (molecule possesses mirror symmetry). Least-squares refinement on 1075 observed reflections (I > 3 sigma(I)) converged with R = 0.0357 and R(w) = 0.0478.