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

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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(OtBu)3 and subsequent hydrolysis provides the bismuth oxido cluster [Bi4O2{OCMe2(2-C4H3S)}8] (2). In contrast, the reaction of Bi(OtBu)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[1 with 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 bismuth⋯π heteroarene interactions, whereas for the pyrrole derivative 6 the dispersion type interactions provide separated dimers.

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

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Publication details

The article was received on 21 Apr 2017, accepted on 02 Jun 2017 and first published on 02 Jun 2017


Article type: Paper
DOI: 10.1039/C7DT01437F
Citation: Dalton Trans., 2017, Advance Article
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    Heteroaryl bismuthines: a novel synthetic concept and metal⋯π heteroarene interactions

    A. M. Preda, W. B. Schneider, M. Rainer, T. Rüffer, D. Schaarschmidt, H. Lang and M. Mehring, Dalton Trans., 2017, Advance Article , DOI: 10.1039/C7DT01437F

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