Large Equatorial Ligand Effects on C-H Bond Activation by Nonheme Iron(IV)-oxo Complexes
(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)
Please use this url to cite or link to this publication:
https://lup.lub.lu.se/record/4368259
- author
- Sun, Xiaoli ; Geng, Caiyun ; Huo, Ruiping ; Ryde, Ulf LU ; Bu, Yuxiang and Li, Jilai LU
- organization
- publishing date
- 2014
- 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
- 2023-04-06 19:16:46
@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}}, }