American Chemical Society
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Oligomerization and Oxide Formation in Bismuth Aryl Alkoxides:  Synthesis and Characterization of Bi44-O)(μ-OC6F5)63-OBi(μ-OC6F5)3}2(C6H5CH3), Bi84-O)23-O)2(μ-OC6F5)16, Bi63-O)43-OC6F5){μ3-OBi(OC6F5)4}3, NaBi43-O)2(OC6F5)9(THF)2, and Na2Bi43-O)2(OC6F5)10(THF)2

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journal contribution
posted on 1999-12-18, 00:00 authored by Kenton H. Whitmire, Silke Hoppe, Orson Sydora, Jennifer L. Jolas, Carolyn M. Jones
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:  Bi44-O)(μ-OR)63-OBi(μ-OR)3}2(C6H5CH3) (2), Bi84-O)23-O)22-OR)16 (3), Bi63-O)43-OR){μ3-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 NaBi43-O)2(OR)9(THF)2 (5) and Na2Bi43-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 26 the single-crystal X-ray structures were determined. Variable-temperature NMR spectra are reported for 2, 3, and 5.