Institut für Anorganische Chemie, RWTH Aachen University, Landoltweg 1, 52056, Aachen, Germany.
Institut für Physikalische Chemie, RWTH Aachen University, Landoltweg 2, 52056, Aachen, Germany.
Angew Chem Int Ed Engl. 2016 Oct 10;55(42):13321-13325. doi: 10.1002/anie.201607131.
The significance of inorganic main-group polymers is demonstrated most clearly by the commercial relevance of polysiloxanes (silicones). Organoboron-based materials such as π-conjugated organoborane polymers and BN-doped polycyclic aromatic hydrocarbons are currently attracting considerable attention. Surprisingly, poly(iminoborane)s (PIBs; [BRNR'] ), that is, the parent unsaturated BN polymers, which are formally isoelectronic to polyacetylene, have not been convincingly characterized thus far. Herein, we present the synthesis and comprehensive characterization of a linear oligo(iminoborane), which comprises a chain of 12-14 BN units on average. With our synthetic approach, unwanted side reactions that result in borazine formation are effectively suppressed. Supporting DFT and TD-DFT calculations provide deeper insight into the microstructure and the electronic structure of the oligomer.
无机主族聚合物的重要性在聚硅氧烷（硅酮）的商业相关性中表现得最为明显。基于有机硼的材料，如π共轭有机硼聚合物和 BN 掺杂的多环芳烃，目前正引起相当大的关注。令人惊讶的是，聚（亚氨基硼烷）（PIBs；[BRNR']），即不饱和 BN 聚合物的母体，与聚乙炔在形式上是等电子的，迄今为止尚未得到令人信服的表征。在此，我们提出了一种线性低聚（亚氨基硼烷）的合成和综合表征，该低聚体平均包含 12-14 个 BN 单元的链。通过我们的合成方法，可以有效地抑制导致形成硼氮烷的副反应。支持 DFT 和 TD-DFT 计算为低聚物的微观结构和电子结构提供了更深入的了解。
