Highly Isoselective Coordination Polymerization of ortho-Methoxystyrene with β-Diketiminato Rare-Earth-Metal Precursors
Highly Isoselective Coordination Polymerization of ortho-Methoxystyrene with β-Diketiminato Rare-Earth-Metal Precursors
复制标题
邻甲氧基苯乙烯与β-二酮基稀土金属前体的高度同选择性配位聚合
DOI：
10.1002/anie.201412166
复制
发表时间：
2015-04-20
影响因子：
16.6
通讯作者：
Cui, Dongmei
中科院分区：
文献类型：
--
作者：
Liu, Dongtao;Yao, Changguang;Cui, Dongmei
本文首次利用阳离子-双酮-稀土金属材料实现了极性邻甲氧基苯乙烯的立体选择配位/插入聚合。活性高，等选择性好（mmmm - >99%）。未遮挡的刘易斯碱性甲氧基不会毒害刘易斯酸性金属中心，而是与乙烯基一起通过sigma-pi螯合激活聚合，因此与缺乏甲氧基的苯乙烯衍生物相比，配位能和活化能更低。
Stereoselective coordination/insertion polymerization of the polar ortho-methoxystyrene has been achieved for the first time by using the cationic beta-diketiminato rare-earth-metal species. High activity and excellent isoselectivity (mmmm>99%) were acheived. The unmasked Lewis-basic methoxy group does not poison the Lewis-acidic metal center, but instead activates the polymerization through sigma-pi chelation to the active species together with the vinyl group, thus lower the coordination and activation energies as compared with those of styrene derivatives lacking the methoxy group.