半夹心稀土金属二烷基配合物催化罗勒烯聚合反应中的区域和立体化学控制
Regio- and Stereochemical Control in Ocimene Polymerization by Half-Sandwich Rare-Earth Metal Dialkyl Complexes.
作者信息
Peng Deqian, Du Gaixia, Zhang Pengfei, Yao Bo, Li Xiaofang, Zhang Shaowen
机构信息
Key Laboratory of Cluster Science of Ministry of Education, School of Chemistry, Beijing Institute of Technology, Beijing, 100081, P. R. China.
出版信息
Macromol Rapid Commun. 2016 Jun;37(12):987-92. doi: 10.1002/marc.201600102. Epub 2016 May 6.
The polymerization of ocimene has been first achieved by half-sandwich rare-earth metal dialkyl complexes in combination with activator and Al(i) Bu3 . The regio- and stereoselectivity in the ocimene polymerization can be controlled by tuning the cyclopentadienyl ligand and the central metal of the complex. The chiral cyclopentadienyl-ligated Sc complex 1 prepares syndiotactic cis-1,4-polyocimene (cis-1,4-selectivity up to 100%, rrrr = 100%), while the corresponding Lu, Y, and Dy complexes 2-4 and the achiral pentamethylcyclopentadienyl Sc, Lu, and Y complexes 5-7 afford isotactic trans-1,2-polyocimenes (trans-1,2-selectivity up to 100%, mm = 100%).
罗勒烯的聚合反应首次通过半夹心稀土金属二烷基配合物与活化剂和三异丁基铝（Al(i)Bu3）相结合实现。罗勒烯聚合反应中的区域选择性和立体选择性可通过调节环戊二烯基配体和配合物的中心金属来控制。手性环戊二烯基配位的钪配合物1可制备间同立构的顺式-1,4-聚罗勒烯（顺式-1,4-选择性高达100%，rrrr = 100%），而相应的镥、钇和镝配合物2-4以及非手性的五甲基环戊二烯基钪、镥和钇配合物5-7则可得到全同立构的反式-1,2-聚罗勒烯（反式-1,2-选择性高达100%，mm = 100%）。
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