Oligomerization and Oxide Formation in Bismuth Aryl Alkoxides:  Synthesis and Characterization of Bi₄(μ₄-O)(μ-OC₆F₅)₆{μ₃-OBi(μ-OC₆F₅)₃}₂(C₆H₅CH₃), Bi₈(μ₄-O)₂(μ₃-O)₂(μ-OC₆F₅)₁₆, Bi₆(μ₃-O)₄(μ₃-OC₆F₅){μ₃-OBi(OC₆F₅)₄}₃, NaBi₄(μ₃-O)₂(OC₆F₅)₉(THF)₂, and Na₂Bi₄(μ₃-O)₂(OC₆F₅)₁₀(THF)₂

Abstract

Exposing [Bi(OR)3(toluene)]2 (1, R = OC6F5) to different solvents leads to the formation of larger polymetallic bismuth oxo alkoxides via ether elimination/oligomerization reactions. Three different compounds were obtained depending upon the conditions: Bi4(mu 4-O)(mu-OR)6(mu 3-OBi(mu-OR)3)2(C6H5CH3) (2), Bi8(mu 4-O)2(mu 3-O)2(mu 2-OR)16 (3), Bi6(mu 3-O)4(mu 3-OR)(mu 3-OBi(OR)4)3 (4). Compounds 2 and 3 can also be synthesized via an alcoholysis reaction between BiPh3 and ROH in refluxing dichloromethane or chloroform. Related oxo complexes NaBi4(mu 3-O)2(OR)9(THF)2 (5) and Na2Bi4(mu 3-O)2(OR)10(THF)2 (6) were obtained from BiCl3 and NaOR in THF. The synthesis of 1 and Bi(OC6Cl5)3 via salt elimination was successful when performed in toluene as solvent. For compounds 2-6 the single-crystal X-ray structures were determined. Variable-temperature NMR spectra are reported for 2, 3, and 5.