Heteroaryl bismuthines: a novel synthetic concept and metal⋯π heteroarene interactions

Abstract

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 bismuth⋯π 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 P, 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 bismuth⋯π heteroarene interactions, whereas for the pyrrole derivative 6 the dispersion type interactions provide separated dimers.