Sterically crowded aryl bismuth compounds: synthesis and characterization of bis{2,4,6-tris(trifluoromethyl)phenyl} bismuth chloride and tris{2,4,6-tris(trifluoromethyl)phenyl} bismuth

The reactions of BiCl3 with 2,4,6-tris(trifluoromethyl)phenyl lithium (LiRf) in ether solution in 1 : 2 and 1 : 3 ratios have led to the isolation of Bi(Rf)2Cl (I) and Bi(Rf)3 (II). The hexane-soluble compounds have been spectroscopically and structurally characterized I: monoclinic space group P21/c, a = 8.816(2), b = 30.459(6), c = 8.817(2)Å, β = 109.58(2)°, Z = 4, V = 2230.7(8)Å3;II: monoclinic space group P21/c, a = 11.769(2), b = 17.029(3), c = 16.213(3)Å, β = 102.74(3)°, Z = 4, V = 3169.3(10)Å3. Both compounds are monomeric in the solid state. Compound II is unstable in solution even under inert atmosphere producing RfH. In the solid state the compound is stable in inert atmosphere but decomposes slowly upon exposure to air producing RfOH and (Rf)2O. In the presence of BiCl3, II undergoes exchange to produce I and another complex which is probably Bi(Rf)Cl2.