Studies on Ring-Opening Metathesis Polymerization of Norborene Catalyzed by Hydride Containing Mononuclear Ruthenium Complex

doi:10.6023/A14100695

Acta Chim. Sinica ›› 2014, Vol. 72 ›› Issue (11): 1144-1146.DOI: 10.6023/A14100695 Previous Articles Next Articles

Communication

含负氢配体的单核钌催化的降冰片烯开环易位聚合催化研究

陈锦森, 朱聪之, 陈勋, 王金虎, 朱进

南京大学化学化工学院微结构国家实验室配位化学国家重点实验室高分子科学与工程系南京 210093

投稿日期:2014-10-09 发布日期:2014-10-10
通讯作者: 朱进 E-mail:jinz@nju.edu.cn
基金资助:
项目受国家自然科学基金(No. 21274058)和国家重点基础研究发展计划(No. 2011CB935801)资助.

Studies on Ring-Opening Metathesis Polymerization of Norborene Catalyzed by Hydride Containing Mononuclear Ruthenium Complex

Chen Jinsen, Zhu Congzhi, Chen Xun, Wang Jinhu, Zhu Jin

Department of Polymer Science and Engineering, School of Chemistry and Chemical Engineering, State Key Laboratory of Coordination Chemistry, Nanjing National Laboratory of Microstructures, Nanjing University, Nanjing 210093, China

Received:2014-10-09 Published:2014-10-10
Supported by:
Project supported by the National Natural Science Foundation of China (No. 21274058) and the National Basic Research Program of China (No. 2011CB935801).

1. Studies on Ring-Opening Metathesis Polymerization of Norborene Catalyzed by Hydride Containing Mononuclear Ruthenium Complex.PDF(299KB)

Abstract

Ring-opening metathesis polymerization (ROMP) has emerged as an important tool for the preparation of architecturally unique macromolecules from cyclic olefins. A wide variety of catalytic systems, ranging from simple metal salts to highly sophisticated alkylidene metal complexes, have been used for the achievement of this synthetically useful transformation. Especially, tremendous efforts have been directed toward the ruthenium-based catalytic systems as well as the understanding of their reactivity patterns. And Grubbs catalysts represent the ultimate in terms of activity, but they are not cost effective due to the sophisticated ligand. Therefore, alternative catalyst precursors that are more readily accessible have been and are still being actively developed. Therefore, a hydride ligand containing mononuclear ruthenium complex Ru(p-cymene)HClPCy₃ reported here was designed to catalyze ring-opening metathesis polymerization of norbornene with high activity. The hydride ligand is critical based on its high trans effect (for ligand dissociation) and the ability to generate carbene species through plausible migratory insertion and α-elimination steps. This catalytic system bearing hydride ligand could be an alternative for the well-defined Ru-based initiators which rules out the need of installation of complex ancillary ligands like NHC or O-Ligand in the coordination sphere or the need of activation with diazo compounds in the search for novel active catalytic species. Further study on the catalytic polymerization activity of Ru(p-cymene)H₂PCy₃ compared to the Ru(p-cymene)HClPCy₃ system revealed that chloride ligand was also crucial to the hydride containing mononuclear ruthenium system, which contains easily dissociated ligand p-cymene and large phosphine ligand that stabilizes the metal complex. And the possible mechanism for the reaction was proposed.

Key words: ring-opening metathesis polymerization, norbornene, hydride ligand

Cite this article

Chen Jinsen, Zhu Congzhi, Chen Xun, Wang Jinhu, Zhu Jin. Studies on Ring-Opening Metathesis Polymerization of Norborene Catalyzed by Hydride Containing Mononuclear Ruthenium Complex[J]. Acta Chim. Sinica, 2014, 72(11): 1144-1146.

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含负氢配体的单核钌催化的降冰片烯开环易位聚合催化研究

Studies on Ring-Opening Metathesis Polymerization of Norborene Catalyzed by Hydride Containing Mononuclear Ruthenium Complex

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