Heteroaryl bismuthines: a novel synthetic concept and metalπ heteroarene interactions

The alkoxide Bi[OCMe₂(2-C₄H₃S)]₃ (1) is formed by the reaction of three equiv. of the alcohol HOCMe₂(2-C₄H₃S) with Bi(O^tBu)₃ and subsequent hydrolysis provides the bismuth oxido cluster [Bi₄O₂{OCMe₂(2-C₄H₃S)}₈] (2). In contrast, the reaction of Bi(O^tBu)₃ and Bi[N(SiMe₃)₂]₃ with the silanols HOSiMe₂(2-C₄H₃X) (X = O, S, Se, and NMe), HOSiMe₂(2-C₄H₂S-5-SiMe₃) and HOSiMe₂(3-C₄H₃S) leads to the formation of tris(heteroaryl)bismuthines Bi(2-C₄H₂X-5-R)₃ [where X = O, R = H (3); X = S, R = H (4); X = S, R = SiMe₃ (5); X = NMe, R = H (6); X = Se, R = H (7)] and Bi(3-C₄H₃S)₃ (8). For the silanols, bismuth-carbon bond formation is observed rather than silanol-alcoholate or silanol-amide exchange. The structures of compounds 1, 2, and 4-7a in the solid state were established by single crystal X-ray diffraction and all compounds except 5 show London dispersion type bismuthπ heteroarene interactions. For the bismuthine Bi(2-C₄H₃Se)₃ (7), two polymorphs were isolated depending on the conditions of crystallization. At 8 °C, polymorph I (7a) crystallizes from an n-hexane solution in the triclinic space group P1[combining macron], whereas polymorph II (7b) crystallizes at 20 °C from a CH₂Cl₂/n-pentane solution in the monoclinic space group P2₁/c. The heteroaryl bismuthines 3 and 4 exhibit 2D network structures as a result of bismuthπ heteroarene interactions, whereas for the pyrrole derivative 6 the dispersion type interactions provide separated dimers.