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Large Equatorial Ligand Effects on C-H Bond Activation by Nonheme Iron(IV)-oxo Complexes

Sun, Xiaoli; Geng, Caiyun; Huo, Ruiping; Ryde, Ulf LU ; Bu, Yuxiang and Li, Jilai LU (2014) In The Journal of Physical Chemistry Part B 118(6). p.1493-1500
Abstract
In this article, we present density functional theory (DFT) calculations on the iron(IV)-oxo catalyzed methane C-H activation reactions for complexes in which the Fe-IV=O core is surrounded by five negatively charged ligands. We found that it follows a hybrid pathway that mixes features of the classical sigma- and pi-pathways in quintet surfaces. These calculations show that the Fe-O-H arrangement in this hybrid pathway is bent in sharp contrast to the collinear character as observed for the classical quintet sigma-pathways before. The calculations have also shown that it is the equatorial ligands that play key roles in tuning the reactivity of Fe-IV=O complexes. The strong pi-donating equatorial ligands employed in the current study cause... (More)
In this article, we present density functional theory (DFT) calculations on the iron(IV)-oxo catalyzed methane C-H activation reactions for complexes in which the Fe-IV=O core is surrounded by five negatively charged ligands. We found that it follows a hybrid pathway that mixes features of the classical sigma- and pi-pathways in quintet surfaces. These calculations show that the Fe-O-H arrangement in this hybrid pathway is bent in sharp contrast to the collinear character as observed for the classical quintet sigma-pathways before. The calculations have also shown that it is the equatorial ligands that play key roles in tuning the reactivity of Fe-IV=O complexes. The strong pi-donating equatorial ligands employed in the current study cause a weak pi(FeO) bond and thereby shift the electronic accepting orbitals (EAO) from the vertically orientated O p(z) orbital to the horizontally orientated O p(x). In addition, all the equatorial ligands are small in size and would therefore be expected have small steric effects upon substrate horizontal approaching. Therefore, for the small and strong g-donating equatorial ligands, the collinear Fe-O-H arrangement is not the best choice for the quintet reactivity. This study adds new element to iron(IV)-oxo catalyzed C-H bond activation reactions. (Less)
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author
organization
publishing date
type
Contribution to journal
publication status
published
subject
in
The Journal of Physical Chemistry Part B
volume
118
issue
6
pages
1493 - 1500
publisher
The American Chemical Society
external identifiers
  • wos:000331493100004
  • scopus:84894099689
ISSN
1520-5207
DOI
10.1021/jp410727r
language
English
LU publication?
yes
id
62443ba5-dc57-427e-aee7-47a1d0e83bee (old id 4368259)
date added to LUP
2014-04-16 13:25:34
date last changed
2017-09-10 04:12:01
@article{62443ba5-dc57-427e-aee7-47a1d0e83bee,
  abstract     = {In this article, we present density functional theory (DFT) calculations on the iron(IV)-oxo catalyzed methane C-H activation reactions for complexes in which the Fe-IV=O core is surrounded by five negatively charged ligands. We found that it follows a hybrid pathway that mixes features of the classical sigma- and pi-pathways in quintet surfaces. These calculations show that the Fe-O-H arrangement in this hybrid pathway is bent in sharp contrast to the collinear character as observed for the classical quintet sigma-pathways before. The calculations have also shown that it is the equatorial ligands that play key roles in tuning the reactivity of Fe-IV=O complexes. The strong pi-donating equatorial ligands employed in the current study cause a weak pi(FeO) bond and thereby shift the electronic accepting orbitals (EAO) from the vertically orientated O p(z) orbital to the horizontally orientated O p(x). In addition, all the equatorial ligands are small in size and would therefore be expected have small steric effects upon substrate horizontal approaching. Therefore, for the small and strong g-donating equatorial ligands, the collinear Fe-O-H arrangement is not the best choice for the quintet reactivity. This study adds new element to iron(IV)-oxo catalyzed C-H bond activation reactions.},
  author       = {Sun, Xiaoli and Geng, Caiyun and Huo, Ruiping and Ryde, Ulf and Bu, Yuxiang and Li, Jilai},
  issn         = {1520-5207},
  language     = {eng},
  number       = {6},
  pages        = {1493--1500},
  publisher    = {The American Chemical Society},
  series       = {The Journal of Physical Chemistry Part B},
  title        = {Large Equatorial Ligand Effects on C-H Bond Activation by Nonheme Iron(IV)-oxo Complexes},
  url          = {http://dx.doi.org/10.1021/jp410727r},
  volume       = {118},
  year         = {2014},
}