Oligomerization and oxide formation in bismuth aryloxides: Synthesis, characterization, and structures of [NaBi(OC6F5)(4)(THF)](infinity) and Na4Bi2(mu(6)-O)(OC6F5)(8)(THF)(4)

The reaction of [Bi(ORf)(3).C7H8](2) (R-f = C6F5) with sodium pentafluorophenolate leads to two new mixed-metal aryloxide complexes depending upon stoichiometry. Using 1 equiv of NaORf per bismuth atom, a polymeric chain with the formula [NaBi(OC6F5)(4)(THF)]infinity, 1, was isolated. If 2 equiv of NaORf is used, the heterometallic oxo/aryloxide Na4Bi2(mu(6)-O)(OC6F5)(8)(THF)(4), 2, is formed. The mass spectroscopic data confirms the elimination of the bis(pentafluorophenyl) ether, RfORf, concomitant with oxo-ligand formation. The compounds have been characterized spectroscopically and by single-crystal X-ray diffraction: Compound 1 crystallizes in the chiral monoclinic space group P2(1), with a = 12.324(2) Angstrom, b = 10.934(2) Angstrom, c = 13.334(3) Angstrom, beta = 91.19(3)degrees, V = 1796.4(6) Angstrom(3), and Z = 2. The polymeric chain in 1 sits about the 2-fold screw axis and is the source of chirality for the compound. Compound 2 crystallizes in the triclinic space group P (1) over bar, with a = 14.059(3) Angstrom, b = 14.060(3) Angstrom, c = 11.531(2) Angstrom, alpha = 108.47(3)degrees, beta = 102.78(3)degrees, gamma = 108.61(3)degrees, V = 1912.6(7) Angstrom(3), and Z = 1 and shows occupational disorder of the sodium and bismuth atom positions. Variable-temperature F-19-NMR studies show dynamic behavior of these bismuth aryloxide complexes in solution.