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Mechanistic insights into regioselective polymerization of 1,3‐Dienes catalyzed by a bipyridine‐ligated iron complex: A DFT study
Author(s) -
Luo Lun,
Kang Xiaohui,
Zhou Guangli,
Chen Si,
Luo Gen,
Qu Jingping,
Luo Yi
Publication year - 2016
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.25167
Subject(s) - regioselectivity , chemistry , bipyridine , steric effects , cationic polymerization , ligand (biochemistry) , polymerization , 2,2' bipyridine , photochemistry , catalysis , polymer chemistry , stereochemistry , crystallography , organic chemistry , polymer , crystal structure , biochemistry , receptor
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.