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,Angewandte Chemie International Edition

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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
Angewandte Chemie International Edition ( IF 16.1 ) Pub Date : 2021-08-05 , DOI: 10.1002/anie.202108032
Shiori Sakamoto ₁ , Tsuyoshi Taniguchi ₂ , Yoko Sakata ₃ , Shigehisa Akine ₄ , Tatsuya Nishimura ₁ , Katsuhiro Maeda ₄

Affiliation

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 give cis-stereoregular poly(phenylacetylene) with a well-controlled molecular weight.

中文翻译：

带有芳基取代的 1,3,5-己三烯链的铑 (I) 配合物：苯乙炔活性聚合的催化剂和 1,3,5-己三烯的潜在螺旋手性

通过（双环[2.2.1]庚-2,5-二烯）氯化铑（I）二聚体（ [Rh(nbd)Cl] ₂) 与芳基硼酸和二苯乙炔在 50% KOH 水溶液的存在下。分离出的复合物的 X 射线晶体学分析表明方形平面结构通过与具有螺旋结构的 1,3,5-己三烯链上的芳基之一强相互作用而稳定。已证实分离的铑配合物的螺旋手性足够稳定，可以在室温下在手性固定相上通过 HPLC 拆分为对映异构体。证实分离的铑配合物可作为苯乙炔活性聚合的引发剂，得到具有良好控制的分子量的顺式立体规则聚（苯乙炔）。

更新日期：2021-09-27

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