[Rh(L-alaninate)(1,5-Cyclooctadiene)] Catalyzed Helix-Sense-Selective Polymerizations of Achiral Phenylacetylenes

Qingyu Wang; Hongge Jia; Yongqiang Shi; Liqun Ma; Guoxing Yang; Yazhen Wang; Shuangping Xu; Jianjun Wang; Yu Zang; Toshiki Aoki

doi:10.3390/polym10111223

[Rh(L-alaninate)(1,5-Cyclooctadiene)] Catalyzed Helix-Sense-Selective Polymerizations of Achiral Phenylacetylenes

Polymers (Basel). 2018 Nov 3;10(11):1223. doi: 10.3390/polym10111223.

Authors

Qingyu Wang¹, Hongge Jia², Yongqiang Shi³, Liqun Ma⁴, Guoxing Yang⁵, Yazhen Wang⁶, Shuangping Xu⁷, Jianjun Wang⁸, Yu Zang⁹, Toshiki Aoki^{10

11}

Affiliations

¹ College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, Heilongjiang Province Key Laboratory of Polymeric Composition Material, Qiqihar University, Qiqihar 161006, China. [email protected].
² College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, Heilongjiang Province Key Laboratory of Polymeric Composition Material, Qiqihar University, Qiqihar 161006, China. [email protected].
³ Department of Materials Science and Engineering and The Shenzhen Key Laboratory for Printed Organic Electronics, South University of Science and Technology of China, Shenzhen 518055, China. [email protected].
⁴ College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, Heilongjiang Province Key Laboratory of Polymeric Composition Material, Qiqihar University, Qiqihar 161006, China. [email protected].
⁵ Daqing Petrochemical Research Center, Petrochemical Research Institute, China National Petroleum Corporation, Daqing 163714, China. [email protected].
⁶ College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, Heilongjiang Province Key Laboratory of Polymeric Composition Material, Qiqihar University, Qiqihar 161006, China. [email protected].
⁷ College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, Heilongjiang Province Key Laboratory of Polymeric Composition Material, Qiqihar University, Qiqihar 161006, China. [email protected].
⁸ College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, Heilongjiang Province Key Laboratory of Polymeric Composition Material, Qiqihar University, Qiqihar 161006, China. [email protected].
⁹ College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, Heilongjiang Province Key Laboratory of Polymeric Composition Material, Qiqihar University, Qiqihar 161006, China. [email protected].
¹⁰ College of Materials Science and Engineering, College of Chemistry and Chemical Engineering, Heilongjiang Province Key Laboratory of Polymeric Composition Material, Qiqihar University, Qiqihar 161006, China. [email protected].
¹¹ Graduate School of Science and Technology, Niigata University, Niigata 950-2181, Japan. [email protected].

Abstract

The [Rh(L-alaninate)(cod)] (cod = 1,5-Cyclooctadiene) complex was synthesized and characterized. Asymmetric polymerizations of achiral phenylacetylene with two hydroxyl groups and a dodecyl group (DoDHPA) were performed by using the rhodium complex as the catalyst to provide polymers with a higher molecular weight (>10⁵) than the polymers obtained using the [Rh(cod)Cl]₂ initiator systems. The resulting polymers showed circular dichroism (CD) signals at approximately 310 and 470 nm, indicating that they have a preferential one-handed helical structure. The helix sense in the polymer main chain was controlled by the sign of the catalyst chirality. These findings suggest that the rhodium complex with a chiral amine is the true active species for the helix-sense-selective polymerization of DoDHPA. The [Rh(L-alaninate)(cod)] complex also exhibits high catalytic activity in the polymerization of phenylacetylene (PA) to give a high yield and molecular weight. All these results demonstrate that this Rh complex is an excellent catalyst for the polymerization of phenylacetylene monomers.

Keywords: L-alaninate; chiral rhodium catalyst; helix-sense-selective polymerization; phenylacetylene.