Rhodium(I) Complexes Bearing an Aryl-Substituted 1,3,5-Hexatriene Chain: Catalysts for Living Polymerization of Phenylacetylene and Potential Helical Chirality of 1,3,5-Hexatrienes
Rhodium(I) Complexes Bearing an Aryl-Substituted 1,3,5-Hexatriene Chain: Catalysts for Living Polymerization of Phenylacetylene and Potential Helical Chirality of 1,3,5-Hexatrienes
复制标题
带有芳基取代的 1,3,5-六三烯链的铑(I)配合物：苯乙炔活性聚合催化剂和 1,3,5-六三烯的潜在螺旋手性
DOI：
10.1002/ange.202108032
复制
发表时间：
2021
期刊：
影响因子：
--
通讯作者：
Katsuhiro Maeda
中科院分区：
文献类型：
--
作者：
Shiori Sakamoto;Tsuyoshi Taniguchi;Yoko Sakata;Shigehisa Akine;Tatsuya Nishimura;Katsuhiro Maeda
在50%氢氧化钾水溶液中，由（二环[2.2.1]庚-2，5-二烯）氯化铑（I）二聚体（[Rh（nbd）Cl]2）与芳基硼酸和二苯基乙炔反应，合成了一种独特的具有芳基取代的1，3，5-己三烯链的工作台稳定铑（I）配合物。对分离的复合物的X射线晶体学分析表明，通过与具有螺旋结构的1，3，5-己三烯链上的芳基之一的强相互作用来稳定正方形平面结构。的螺旋手性的分离铑配合物被证实是足够稳定的手性固定相在室温下通过HPLC拆分成对映异构体。研究结果表明，该铑配合物可作为引发剂引发苯乙炔的活性聚合，得到分子量可控的无规立构聚苯乙炔。
Unique bench‐stable rhodium(I) complexes bearing an aryl‐substituted 1,3,5‐hexatriene chain have been synthesized by reactions of (bicyclo[2.2.1]hepta‐2,5‐diene)rhodium(I) chloride dimer ([Rh(nbd)Cl]2) with aryl boronic acids and diphenylacetylenes in the presence of a 50 % aqueous solution of KOH. X‐ray crystallographic analysis of the isolated complexes indicated a square‐planar structure stabilized by a strong interaction with one of the aryl groups on the 1,3,5‐hexatriene chain, which has a helical structure. The helical chirality of the isolated rhodium complexes was confirmed to be sufficiently stable to be resolved into enantiomers by HPLC on a chiral stationary phase at room temperature. It was confirmed that the isolated rhodium complexes functioned as initiators for living polymerization of phenylacetylene to givecis‐stereoregular poly(phenylacetylene) with a well‐controlled molecular weight.