Aggregation and Hydrolysis Reactions of Bismuth Alkoxides

Abstract

ABSTRACTNew bismuth alkoxide and oxo-alkoxide complexes have been prepared from the salt metathesis reaction of NaOR with BiCl3. When R = CH(CF3)2, the product is [Bi(μ- OR)(OR)2(THF)]2 Similar work with R = C6F5 has not yielded a simple alkoxide, but complexes of formulation NaBi3(μ3-O)(OR)8(THF), NaBi4((μ3-O)2(OR)9(THF)2, Na2Bi4(μ3- O)2(OR)10 and Bi6(μ3 -OR)(μ3 -O)4[μ3-OBi(OR)4]3 have been observed. The reaction of BiPh3 with HOC6F5, however, did produce the desired alkoxide which has been characterized as [Bi(OR)2(μ-OR)(toluene)]2 and [Bi(OR)2(μ-OR)(toluene)[2.2 toluene. The reaction of this alkoxide with NaOC6F5 led to the production of Bi6(ν3--O)2 (μ4-O)(OR)12 and NaBi3(μ3- O)(OR)8(THF)3. Reaction of BiPh3 with HOC6F5 in THF led to the formation of Bi6(μ3-OR)(μ3-O)4[μ3-OBi(OR)4]3 (THiF)2. Surprisingly the reaction of BiEt3 and HOR (R = C6F5 or Ph) displaced only one Et group to give [Et2Bi(μ-OR)]∞ which exist as infinite chain polymers with alternating Bi-O-Bi backbones. These spiral chains form chiral helices in the crystal lattice.