Tepper Ronny, Schulze Benjamin, Jäger Michael, Friebe Christian, Scharf Daniel H, Görls Helmar, Schubert Ulrich S
†Laboratory of Organic and Macromolecular Chemistry (IOMC), Friedrich Schiller University Jena, Humboldtstr. 10, 07743 Jena, Germany.
‡Jena Center for Soft Matters (JCSM), Friedrich Schiller University Jena, Philosophenweg 7, 07743 Jena, Germany.
J Org Chem. 2015 Mar 20;80(6):3139-50. doi: 10.1021/acs.joc.5b00028. Epub 2015 Mar 3.
A systematic series of anion receptors based on bidentate halogen bonding by halo-triazoles and -triazoliums is presented. The influence of the halogen bond donor atom, the electron-withdrawing group, and the linker group that bridges the two donor moieties is investigated. Additionally, a comparison with hydrogen bond-based analogues is provided. A new, efficient synthetic approach to introduce different halogens into the heterocycles is established using silver(I)-triazolylidenes, which are converted to the corresponding halo-1,2,3-triazoliums with different halogens. Comprehensive nuclear magnetic resonance binding studies supported by isothermal titration calorimetry studies were performed with different halides and oxo-anions to evaluate the influence of key parameters of the halogen bond donor, namely, polarization of the halogen and the bond angle to the anion. The results show a larger anion affinity in the case of more charge-dense halides as well as a general preference of the receptors to bind oxo-anions, in particular sulfate, over halides.
本文介绍了一系列基于卤代三唑和三唑鎓的双齿卤素键合的阴离子受体。研究了卤素键供体原子、吸电子基团以及连接两个供体部分的连接基团的影响。此外，还提供了与基于氢键的类似物的比较。使用银（I）-三唑亚基建立了一种新的、有效的将不同卤素引入杂环的合成方法，该亚基可转化为具有不同卤素的相应卤代-1,2,3-三唑鎓。通过等温滴定量热法研究支持的全面核磁共振结合研究，对不同的卤化物和含氧阴离子进行了研究，以评估卤素键供体的关键参数的影响，即卤素的极化和与阴离子的键角。结果表明，对于电荷密度更高的卤化物，阴离子亲和力更大，并且受体通常更倾向于结合含氧阴离子，特别是硫酸盐，而不是卤化物。
