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Mechanistic study on iron(II)‐mediated direct arylation of benzene with chlorobenzene
Author(s) -
Sun Xiaoli,
Geng Caiyun,
Li Jilai
Publication year - 2019
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.25912
Subject(s) - chlorobenzene , chemistry , density functional theory , benzene , ligand (biochemistry) , diimine , computational chemistry , catalysis , redox , medicinal chemistry , inorganic chemistry , organic chemistry , receptor , biochemistry
Density functional theory calculations on the reaction mechanisms of the direct arylation of benzene with chlorobenzene mediated by a series of low‐valent iron complexes, in which the Fe(II) center is surrounded by different electron‐donor ligands (acetate anion (OAc), baphophenanthroline (baph), 1,10‐phenanthroline (phen), and redox active ligand amidophenolate (ap)) using density functional theory. Fe(II) models, 1b Fe II (baph), 1p Fe II (phen), 1d Fe II (diimine), 2o Fe II (OAc) 2 , 2po Fe II (OAc)(phen), 2p Fe II (phen) 2 as well as 2a Fe II (ap) 2 were established. According to our calculations, 1b and 2a are promising candidates for the direct arylation transformation. The complexes under different ligands show their unique mechanism characteristics. Furthermore, a correlation has been established among the activation barriers, the energy gaps of frontier orbitals, the distortion energies, as well as the reaction enthalpies. The knowledge obtained herein not only deepens our mechanistic understanding of iron‐mediated direct arylation but may also provide guidance for the rational design of catalysts.