Oligomerization and Oxide Formation in Bismuth Aryl Alkoxides: Synthesis and Characterization of Bi<sub>4</sub>(μ<sub>4</sub>-O)(μ-OC<sub>6</sub>F<sub>5</sub>)<sub>6</sub>{μ<sub>3</sub>-OBi(μ-OC<sub>6</sub>F<sub>5</sub>)<sub>3</sub>}<sub>2</sub>(C<sub>6</sub>H<sub>5</sub>CH<sub>3</sub>), Bi<sub>8</sub>(μ<sub>4</sub>-O)<sub>2</sub>(μ<sub>3</sub>-O)<sub>2</sub>(μ-OC<sub>6</sub>F<sub>5</sub>)<sub>16</sub>, Bi<sub>6</sub>(μ<sub>3</sub>-O)<sub>4</sub>(μ<sub>3</sub>-OC<sub>6</sub>F<sub>5</sub>){μ<sub>3</sub>-OBi(OC<sub>6</sub>F<sub>5</sub>)<sub>4</sub>}<sub>3</sub>, NaBi<sub>4</sub>(μ<sub>3</sub>-O)<sub>2</sub>(OC<sub>6</sub>F<sub>5</sub>)<sub>9</sub>(THF)<sub>2</sub>, and Na<sub>2</sub>Bi<sub>4</sub>(μ<sub>3</sub>-O)<sub>2</sub>(OC<sub>6</sub>F<sub>5</sub>)<sub>10</sub>(THF)<sub>2</sub>
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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(μ4-O)(μ-OR)6{μ3-OBi(μ-OR)3}2(C6H5CH3) (2), Bi8(μ4-O)2(μ3-O)2(μ2-OR)16 (3), Bi6(μ3-O)4(μ3-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 NaBi4(μ3-O)2(OR)9(THF)2 (5) and Na2Bi4(μ3-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.
