Oligomerization and oxide formation in bismuth aryl alkoxides: Synthesis and characterization of Bi-4(mu(4)-O)(mu-OC6F5)(6){mu(3)-OBi(mu-OC6F5)(3)}(2)(C6H5CH3), Bi-8(mu(4)-O)(2)(mu(3)-O)(2)(mu-OC6F5)(16), Bi-6(mu(3)-O)(4)(mu(3)-OC6F5){mu(3)-OBi(OC6F5)(4)}(3), NaBi4(mu(3)-O)(2)(OC6F5)(9)(THF)(2), and Na2Bi4(mu(3)-O)(2)(OC6F5)(10)(THF)(2)

Exposing [Bi(OR)(3)(toluene)](2) (1, R = OC6F5) to different solvents leads to the formation of larger polymetallic bismuth oxo alkoxides via ether el imination/oligomerization reactions. Three different compounds were obtaine d depending upon the conditions: Bi-4(mu(4)-O)(mu-OR)(6){mu(3)-OBi(mu-OR)(3 )}(2)(C6H5CH3) (2), Bi-8(mu(4)-O)(2)(mu(3)-O)(2)(mu(2)-OR)(16) (3), Bi-6(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)- (O R)(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 e limination was successful when performed in toluene as solvent. For compoun ds 2-6 the single-crystal X-ray structures were determined. Variable-temper ature NMR spectra are reported for 2, 3, and 5.