Mechanistic insights into regioselective polymerization of 1,3-Dienes catalyzed by a bipyridine-ligated iron complex: A DFT study
Mechanistic insights into regioselective polymerization of 1,3-Dienes catalyzed by a bipyridine-ligated iron complex: A DFT study
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DOI：
10.1002/qua.25167
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发表时间：
2016-09
影响因子：
2.2
通讯作者：
Lun Luo;Xiaohui Kang;Guangli Zhou;Si Chen;Gen Luo;Jingping Qu;Yi Luo
中科院分区：
文献类型：
--
作者：
Lun Luo;Xiaohui Kang;Guangli Zhou;Si Chen;Gen Luo;Jingping Qu;Yi Luo
本文研究了带联吡啶配体的阳离子铁（II）配合物催化异戊二烯和3-甲基戊二烯的区域选择性聚合。计算结果与实验结果一致后，发现开壳层未配对的三维电子不是部分分布在氧化还原活性联吡啶配体上，而是局部分布在Fe中心。与电子因素相比，空间效应对区域选择性的控制作用更大。在烯烃选择性聚合过程中，非环戊二烯基辅助配体在大多数插入过渡态下经常发生变形，但变形能主要由单体和铁烷基部分贡献，而不是由联吡啶配体本身贡献。©2016 Wiley期刊公司
The regioselective polymerizations of isoprene and 3-methyl-pentadiene catalyzed by a cationic iron (II) complex bearing bipyridine ligand have been computationally studied. Having achieved an agreement between calculation and experiment, it is found that the open-shell unpaired 3d-electrons localize on Fe center rather than partially distribute on the redox-active bipyridine ligand. The steric effect plays a more important role in controlling the regioselectivity in comparison with electronic factors. The deformation energy is mainly contributed by monomer and Fe-alkyl moieties rather than the bipyridine ligands themselves, although noncyclopentadienyl ancillary ligands are often deformed in most insertion transition states for selective polymerization of olefin. © 2016 Wiley Periodicals, Inc.