Suraru Sabin-Lucian, Lee Jason A, Luscombe Christine K
Department of Materials Science and Engineering, University of Washington, Seattle, Washington 98195-2120, United States.
Department of Chemistry, University of Washington, Seattle, Washington 98195-1700, United States.
ACS Macro Lett. 2016 Apr 19;5(4):533-536. doi: 10.1021/acsmacrolett.6b00062. Epub 2016 Apr 8.
In the search for new synthetic routes toward greener and more facile syntheses of conjugated polymers, C-H functionalization provides a promising solution by minimizing the production and processing of aryl halide monomer precursors used in traditional organometallic coupling reactions. In this paper, we investigate the use of Au(I) and its ability to directly C-H activate 2-bromo-3-hexylthiophene to form a reactive monomer species, bypassing the typical Grignard monomer formation from a dihalogenated thiophene. Addition of Pd-PEPPSI-iPr as a palladium catalyst source in the presence of the resultant aurylated thiophene monomer yielded poly(3-hexylthiophene) as observed by both NMR and GPC. Studies on the growth of these polymers show linear dependence between and monomer conversion, low dispersities, as well as predicted by catalyst loading, which is supportive of a living-type chain growth mechanism. This Au-Pd system represents a novel methodology for incorporating C-H activation into the synthesis of P3HT with control over .
在寻找更绿色、更简便的共轭聚合物合成新路线时，C-H官能化提供了一种有前景的解决方案，通过减少传统有机金属偶联反应中使用的芳基卤化物单体前体的生产和加工。在本文中，我们研究了Au(I)的用途及其直接C-H活化2-溴-3-己基噻吩以形成反应性单体物种的能力，从而绕过了从二卤代噻吩形成典型格氏单体的过程。在所得的金化噻吩单体存在下，加入Pd-PEPPSI-iPr作为钯催化剂源，通过NMR和GPC观察到生成了聚(3-己基噻吩)。对这些聚合物生长的研究表明， 与单体转化率之间呈线性关系，分散度低，以及由催化剂负载量预测的 ，这支持了活性型链增长机制。这种金-钯体系代表了一种将C-H活化纳入聚3-己基噻吩合成并控制 的新方法。
