Hypervalent tetracoordinate organobismuth compounds (10‐Bi‐4)

A stable hypervalent 10‐Bi‐4 species, tetraethylammonium bis[α,α‐bis(trifluoromethyl)benzenemethanolato(2‐)‐C2],Obismuthanate(1‐), was prepared by the reaction of bismuth trichloride with 2 equiv of lithium 2‐(2‐lithiophenyl)‐2‐propoxide derivatives. The ate complex was inert toward MeI, instead, the corresponding nonfluorinated analogue, bis[α,α‐bis(dimethyl)benzenemethanolato(2‐)‐C2, O]bismuthanate(1‐), was reactive enough toward MeI to give O‐methylated product. Regioselective methylation at the nonfluorinated methanolate was observed in the reaction of unsymmetrically substituted ate complex, [α,α‐bis(dimethyl)benzenemethanolato(2‐)‐C2, O[]α,α‐bis(trifluoromethyl) benzenemethanolato(2‐)‐C2, O]bis‐muthanate(1‐). Mechanism of isomerization of these ate complexes and related protonated compounds and the synthesis and stability of [α,α‐bis(trifluoromethyl)‐benzenemethanolato (2‐) ‐C2, O]diarylbismuthanate‐(1‐) were also described.