Mechanistic insights into regioselective polymerization of 1,3-Dienes catalyzed by a bipyridine-ligated iron complex: A DFT study

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• 作者：Lun Luo ; Xiaohui Kang ; Guangli Zhou ; Si Chen ; Gen Luo ; Jingping Qu and Yi Luo
• 刊名：International Journal of Quantum Chemistry
• 出版年：2016
• 出版时间：September 05, 2016
• 年：2016
• 卷：116
• 期：17
• 页码：1274-1280
• 全文大小：664K
• ISSN：1097-461X

文摘

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.