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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 orcid ; 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
; ; ; ; and
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 (ACS)
external identifiers
  • wos:000331493100004
  • scopus:84894099689
  • pmid:24471414
ISSN
1520-5207
DOI
10.1021/jp410727r
language
English
LU publication?
yes
additional info
The information about affiliations in this record was updated in December 2015. The record was previously connected to the following departments: Theoretical Chemistry (S) (011001039)
id
62443ba5-dc57-427e-aee7-47a1d0e83bee (old id 4368259)
date added to LUP
2016-04-01 14:12:25
date last changed
2025-10-14 09:22:16
@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 (ACS)}},
  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}},
  doi          = {{10.1021/jp410727r}},
  volume       = {{118}},
  year         = {{2014}},
}