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A Computational Comparison of Oxygen Atom Transfer Catalyzed by Dimethyl Sulfoxide Reductase with Mo and W

Li, Jilai; Andrejic, Milica; Mata, Ricardo A. and Ryde, Ulf LU (2015) In European Journal of Inorganic Chemistry p.3580-3589
Abstract
A thorough computational study has been performed to investigate oxygen atom transfer (OAT) reactions catalyzed by dimethyl sulfoxide reductase (DMSOR) with a catalytic molybdenum or tungsten ion. Thirteen different density functional theory (DFT) methods have been employed to obtain structural parameters along the reaction pathway, and single-point energies were computed with local correlation coupled-cluster methods [LCCSD(T0)]. For both Mo and W, most DFT methods indicate that the enzyme follows a twostep mechanism with a stable intermediate in which a DMSO molecule coordinates to the metal ion in the +IV oxidation state, and this is also confirmed by the LCCSD(T0) energies. The W-substituted models have a 26-30 kJ/mol lower activation... (More)
A thorough computational study has been performed to investigate oxygen atom transfer (OAT) reactions catalyzed by dimethyl sulfoxide reductase (DMSOR) with a catalytic molybdenum or tungsten ion. Thirteen different density functional theory (DFT) methods have been employed to obtain structural parameters along the reaction pathway, and single-point energies were computed with local correlation coupled-cluster methods [LCCSD(T0)]. For both Mo and W, most DFT methods indicate that the enzyme follows a twostep mechanism with a stable intermediate in which a DMSO molecule coordinates to the metal ion in the +IV oxidation state, and this is also confirmed by the LCCSD(T0) energies. The W-substituted models have a 26-30 kJ/mol lower activation barrier for the OAT reaction, and the reaction is 6370 kJ/mol more exothermic than that with Mo. Different DFT methods give widely different activation and reaction energies, which roughly depend on the amount of exact exchange in the method; these differences are also reflected in the structures, especially for the rate-limiting transition state. Consequently, there is quite a large variation in energies and various energy corrections (thermal, solvation, dispersion, and relativistic; up to 39 kJ/mol) depending on which DFT method is used to obtain the geometries. Therefore, a mechanism predicted by a single method should be viewed with caution. (Less)
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author
organization
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type
Contribution to journal
publication status
published
subject
keywords
Density functional calculations, Molybdenum, Tungsten, Enzyme models
in
European Journal of Inorganic Chemistry
issue
21
pages
3580 - 3589
publisher
John Wiley & Sons
external identifiers
  • wos:000359297800023
  • scopus:84938204657
ISSN
1099-0682
DOI
10.1002/ejic.201500209
language
English
LU publication?
yes
id
127ec35f-6016-4f52-b621-9f8760b60a39 (old id 7975561)
date added to LUP
2015-09-24 15:07:16
date last changed
2017-09-24 03:13:41
@article{127ec35f-6016-4f52-b621-9f8760b60a39,
  abstract     = {A thorough computational study has been performed to investigate oxygen atom transfer (OAT) reactions catalyzed by dimethyl sulfoxide reductase (DMSOR) with a catalytic molybdenum or tungsten ion. Thirteen different density functional theory (DFT) methods have been employed to obtain structural parameters along the reaction pathway, and single-point energies were computed with local correlation coupled-cluster methods [LCCSD(T0)]. For both Mo and W, most DFT methods indicate that the enzyme follows a twostep mechanism with a stable intermediate in which a DMSO molecule coordinates to the metal ion in the +IV oxidation state, and this is also confirmed by the LCCSD(T0) energies. The W-substituted models have a 26-30 kJ/mol lower activation barrier for the OAT reaction, and the reaction is 6370 kJ/mol more exothermic than that with Mo. Different DFT methods give widely different activation and reaction energies, which roughly depend on the amount of exact exchange in the method; these differences are also reflected in the structures, especially for the rate-limiting transition state. Consequently, there is quite a large variation in energies and various energy corrections (thermal, solvation, dispersion, and relativistic; up to 39 kJ/mol) depending on which DFT method is used to obtain the geometries. Therefore, a mechanism predicted by a single method should be viewed with caution.},
  author       = {Li, Jilai and Andrejic, Milica and Mata, Ricardo A. and Ryde, Ulf},
  issn         = {1099-0682},
  keyword      = {Density functional calculations,Molybdenum,Tungsten,Enzyme models},
  language     = {eng},
  number       = {21},
  pages        = {3580--3589},
  publisher    = {John Wiley & Sons},
  series       = {European Journal of Inorganic Chemistry},
  title        = {A Computational Comparison of Oxygen Atom Transfer Catalyzed by Dimethyl Sulfoxide Reductase with Mo and W},
  url          = {http://dx.doi.org/10.1002/ejic.201500209},
  year         = {2015},
}