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



陈锦森, 朱聪之, 陈勋, 王金虎, 朱进   

  1. 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
  • 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   

  1. 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).

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