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首页> 外文期刊>Dalton transactions: An international journal of inorganic chemistry >Heteroaryl bismuthines: a novel synthetic concept and metal center dot center dot center dot pi heteroarene interactions
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Heteroaryl bismuthines: a novel synthetic concept and metal center dot center dot center dot pi heteroarene interactions

机译：杂志铋：一种新型合成概念和金属中心点中心点中心点PI杂种芳烃相互作用

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摘要

The alkoxide Bi[OCMe2(2-C4H3S)](3) (1) is formed by the reaction of three equiv. of the alcohol HOCMe2(2-C4H3S) with Bi((OBu)-Bu-t)(3) and subsequent hydrolysis provides the bismuth oxido cluster [Bi4O2{OCMe2(2-C4H3S)}(8)] (2). In contrast, the reaction of Bi((OBu)-Bu-t)(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 center dot center dot center dot pi heteroarene interactions. For the bismuthine Bi(2-C4H3Se)(3) (7), two polymorphs were isolated depending on the conditions of crystallization. At 8 degrees C, polymorph I (7a) crystallizes from an n-hexane solution in the triclinic space group P (1) over bar, whereas polymorph II (7b) crystallizes at 20 degrees C from a CH2Cl2/n-pentane solution in the monoclinic space group P2(1)/c. The heteroaryl bismuthines 3 and 4 exhibit 2D network structures as a result of bismuth center dot center dot center dot pi heteroarene interactions, whereas for the pyrrole derivative 6 the dispersion type interactions provide separated dimers.
机译：通过三当量的反应形成醇盐BI [OCME2（2-C4H3S）]（3）（1）。用Bi（（OBU）-Bu-T）（3）和随后的水解提供了羟甲酰胺簇[Bi4O2 {OCME2（2-C4H3S）}（2）的醇Hocme2（2-C4H3）。相反，Bi（（OBU）-Bu-T）（3）和Bi [N（SiME3）（2）]（3）与硅烷醇Hosime2（2-C4H3x）的反应（x = o，s，se和NME），Hosime2（2-C4H2S-5-SIME3）和Hosime2（3-C4H3s）导致Tris（杂芳基）Bi（2-C4H2X-5-R）（3）的形成[其中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）]和BI（3-C4H3）3（8）。对于硅烷醇，观察到铋 - 碳键形成而不是硅烷醇醇或硅烷醇 - 酰胺交换。通过单晶X射线衍射和所有化合物建立固态化合物1,2和4-7a的结构，除了5显示伦敦分散型铋中心点中心点中心点PI杂芳烯相互作用。对于铋酸二铋Bi（2-C4H3Se）（3）（7），根据结晶条件分离两种多晶型物。在8℃下，多晶型I（7a）在三级空间组p（1）中的正己烷溶液中结晶，而多晶型II（7b）在20℃下从CH 2 Cl 2 / N-戊烷溶液中结晶单斜核空间组P2（1）/ c。杂芳基铋3和4表现出2D网络结构作为铋中心点中心点中心点PI杂芳烯相互作用，而对于吡咯衍生物6，分散型相互作用提供分离的二聚体。

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    Preda A. M.; Schneider W. B.; Rainer M.; Rueffer T.; Schaarschmidt D.; Lang H.; Mehring M.;

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    Tech Univ Chemnitz Fak Nat Wissensch Inst Chem Prof Koordinat Chem D-09107 Chemnitz Germany;

    Tech Univ Chemnitz Fak Nat Wissensch Inst Chem Prof Koordinat Chem D-09107 Chemnitz Germany;

    Tech Univ Chemnitz Fak Nat Wissensch Inst Chem Prof Koordinat Chem D-09107 Chemnitz Germany;

    Tech Univ Chemnitz Fak Nat Wissensch Inst Chem Prof Anorgan Chem D-09107 Chemnitz Germany;

    Tech Univ Chemnitz Fak Nat Wissensch Inst Chem Prof Anorgan Chem D-09107 Chemnitz Germany;

    Tech Univ Chemnitz Fak Nat Wissensch Inst Chem Prof Anorgan Chem D-09107 Chemnitz Germany;

    Tech Univ Chemnitz Fak Nat Wissensch Inst Chem Prof Koordinat Chem D-09107 Chemnitz Germany;

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  • 正文语种 eng
  • 中图分类 化学;无机化学;
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