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Isokinetic behaviour in gas phase catalytic haloarene hydrodehalogenation reactions: Mechanistic considerations

Keane, MA and Larsson, Ragnar LU (2006) In Journal of Molecular Catalysis A: Chemical 249(1-2). p.158-165
Abstract
Compensation behaviour is established for the gas phase hydrodehalogenation of a range of haloarenes over a common Ni/SiO2 catalyst. Analysis of the experimental results delivers an isokinetic temperature (T-iso) at 658 +/- 2K associated with the following reactants: chlorobenzene, 4-chlorotoluene, 3-chlorophenol, 1,3,-dichlorobenzene, 4-chlorophenol, 3,5-dichlorophenol, 1,4-dichlorobenzene, bromobenzene, 2,6-dichlorophenol, 2-chlorophenol, 1,2-dichlorobenzene and 1,3-dibromobenzene. The occurrence of a T-iso is accounted for using the Selective Energy Transfer (SET) model that is based on the premise of resonance between a vibrational mode of the catalyst and a vibrational mode of the reactant with a transferral of resonance energy from... (More)
Compensation behaviour is established for the gas phase hydrodehalogenation of a range of haloarenes over a common Ni/SiO2 catalyst. Analysis of the experimental results delivers an isokinetic temperature (T-iso) at 658 +/- 2K associated with the following reactants: chlorobenzene, 4-chlorotoluene, 3-chlorophenol, 1,3,-dichlorobenzene, 4-chlorophenol, 3,5-dichlorophenol, 1,4-dichlorobenzene, bromobenzene, 2,6-dichlorophenol, 2-chlorophenol, 1,2-dichlorobenzene and 1,3-dibromobenzene. The occurrence of a T-iso is accounted for using the Selective Energy Transfer (SET) model that is based on the premise of resonance between a vibrational mode of the catalyst and a vibrational mode of the reactant with a transferral of resonance energy from the catalyst to the reactant to generate the "activated complex" with subsequent reaction. In this study of a single catalyst promoting a common (hydrodehalogenation) reaction for a family of haloarene reactants, we establish the complimentary vibrational modes as the out-plane C-H vibrations of substituted benzene and Ni-H vibration at high hydrogen surface coverage. The proposed surface rate-determining step is the C-H "out-of-plane" activation favouring an sp(2) to sp(3) transformation. (c) 2006 Elsevier B.V. All rights reserved. (Less)
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author
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type
Contribution to journal
publication status
published
subject
keywords
isokinetic temperature, compensation effect, Ni/SiO2, hydrodehalogenation, haloarenes, selective energy transfer model
in
Journal of Molecular Catalysis A: Chemical
volume
249
issue
1-2
pages
158 - 165
publisher
Elsevier
external identifiers
  • wos:000237173500022
  • scopus:33646014795
ISSN
1381-1169
DOI
10.1016/j.molcata.2006.01.017
language
English
LU publication?
yes
id
c0277fda-50ef-417b-9958-d420f2a38937 (old id 410397)
date added to LUP
2016-04-01 16:09:28
date last changed
2020-01-12 19:05:31
@article{c0277fda-50ef-417b-9958-d420f2a38937,
  abstract     = {Compensation behaviour is established for the gas phase hydrodehalogenation of a range of haloarenes over a common Ni/SiO2 catalyst. Analysis of the experimental results delivers an isokinetic temperature (T-iso) at 658 +/- 2K associated with the following reactants: chlorobenzene, 4-chlorotoluene, 3-chlorophenol, 1,3,-dichlorobenzene, 4-chlorophenol, 3,5-dichlorophenol, 1,4-dichlorobenzene, bromobenzene, 2,6-dichlorophenol, 2-chlorophenol, 1,2-dichlorobenzene and 1,3-dibromobenzene. The occurrence of a T-iso is accounted for using the Selective Energy Transfer (SET) model that is based on the premise of resonance between a vibrational mode of the catalyst and a vibrational mode of the reactant with a transferral of resonance energy from the catalyst to the reactant to generate the "activated complex" with subsequent reaction. In this study of a single catalyst promoting a common (hydrodehalogenation) reaction for a family of haloarene reactants, we establish the complimentary vibrational modes as the out-plane C-H vibrations of substituted benzene and Ni-H vibration at high hydrogen surface coverage. The proposed surface rate-determining step is the C-H "out-of-plane" activation favouring an sp(2) to sp(3) transformation. (c) 2006 Elsevier B.V. All rights reserved.},
  author       = {Keane, MA and Larsson, Ragnar},
  issn         = {1381-1169},
  language     = {eng},
  number       = {1-2},
  pages        = {158--165},
  publisher    = {Elsevier},
  series       = {Journal of Molecular Catalysis A: Chemical},
  title        = {Isokinetic behaviour in gas phase catalytic haloarene hydrodehalogenation reactions: Mechanistic considerations},
  url          = {http://dx.doi.org/10.1016/j.molcata.2006.01.017},
  doi          = {10.1016/j.molcata.2006.01.017},
  volume       = {249},
  year         = {2006},
}