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Kinetics of alpha hydrogen abstractions in thiols, sulfides and thiocarbonyl compounds

Aäron Vandeputte UGent, Maarten Sabbe UGent, Marie-Françoise Reyniers UGent and Guy Marin UGent (2012) PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 14(37). p.12773-12793
abstract
Hydrogen abstraction reactions involving organosulfur compounds play an important role in many industrial, biological and atmospheric processes. Despite their chemical relevance, little is known about their kinetics. In this work a group additivity model is developed that allows predicting the Arrhenius parameters for abstraction reactions of alpha hydrogen atoms from thiols, alkyl sulfides, alkyl disulfides and thiocarbonyl compounds by carbon-centered radicals at temperatures ranging from 300 to 1500 K. Rate coefficients for 102 hydrogen abstractions were obtained using conventional transition state theory within the high-pressure limit. Electronic barriers were calculated using the CBS-QB3 method and the rate coefficients were corrected for tunneling and hindered rotation about the transitional bond. Group additivity values for 46 groups are determined. To account for resonance and hyperconjugative stabilization in the transition state, 8 resonance corrections were fitted to a set of 32 reactions. The developed group additivity scheme was validated using a test set containing an additional 30 reactions. The group additivity scheme succeeds in reproducing the rate coefficients on average within a factor of 2.4 at 300 K and 1.4 at 1000 K. Mean absolute deviations of the Arrhenius parameters amount to, respectively, 2.5 kJ mol(-1) for E-a and 0.13 for log A, both at 300 and 1000 K. This work hence illustrates that the recently developed group additivity methods for Arrhenius parameters extrapolate successfully to hetero-element containing compounds.
Please use this url to cite or link to this publication:
author
organization
year
type
journalArticle (original)
publication status
published
subject
keyword
REACTION-RATE PREDICTION, GAS-PHASE THERMOLYSIS, BETA-SCISSION REACTIONS, TRANSITION-STATE THEORY, ACTIVATION-ENERGIES, DIMETHYL SULFIDE, SULFUR-COMPOUNDS, REACTION-RATES, H-ABSTRACTION, AB-INITIO
journal title
PHYSICAL CHEMISTRY CHEMICAL PHYSICS
volume
14
issue
37
pages
12773 - 12793
Web of Science type
Article
Web of Science id
000308101100011
JCR category
PHYSICS, ATOMIC, MOLECULAR & CHEMICAL
JCR impact factor
3.829 (2012)
JCR rank
6/34 (2012)
JCR quartile
1 (2012)
ISSN
1463-9076
DOI
10.1039/C2CP41114H
language
English
UGent publication?
yes
classification
A1
copyright statement
I have transferred the copyright for this publication to the publisher
id
2997433
handle
http://hdl.handle.net/1854/LU-2997433
date created
2012-09-21 15:41:25
date last changed
2013-07-04 13:32:21
@article{2997433,
  abstract     = {Hydrogen abstraction reactions involving organosulfur compounds play an important role in many industrial, biological and atmospheric processes. Despite their chemical relevance, little is known about their kinetics. In this work a group additivity model is developed that allows predicting the Arrhenius parameters for abstraction reactions of alpha hydrogen atoms from thiols, alkyl sulfides, alkyl disulfides and thiocarbonyl compounds by carbon-centered radicals at temperatures ranging from 300 to 1500 K. Rate coefficients for 102 hydrogen abstractions were obtained using conventional transition state theory within the high-pressure limit. Electronic barriers were calculated using the CBS-QB3 method and the rate coefficients were corrected for tunneling and hindered rotation about the transitional bond. Group additivity values for 46 groups are determined. To account for resonance and hyperconjugative stabilization in the transition state, 8 resonance corrections were fitted to a set of 32 reactions. The developed group additivity scheme was validated using a test set containing an additional 30 reactions. The group additivity scheme succeeds in reproducing the rate coefficients on average within a factor of 2.4 at 300 K and 1.4 at 1000 K. Mean absolute deviations of the Arrhenius parameters amount to, respectively, 2.5 kJ mol(-1) for E-a and 0.13 for log A, both at 300 and 1000 K. This work hence illustrates that the recently developed group additivity methods for Arrhenius parameters extrapolate successfully to hetero-element containing compounds.},
  author       = {Vandeputte, A{\"a}ron and Sabbe, Maarten and Reyniers, Marie-Fran\c{c}oise and Marin, Guy},
  issn         = {1463-9076},
  journal      = {PHYSICAL CHEMISTRY CHEMICAL PHYSICS},
  keyword      = {REACTION-RATE PREDICTION,GAS-PHASE THERMOLYSIS,BETA-SCISSION REACTIONS,TRANSITION-STATE THEORY,ACTIVATION-ENERGIES,DIMETHYL SULFIDE,SULFUR-COMPOUNDS,REACTION-RATES,H-ABSTRACTION,AB-INITIO},
  language     = {eng},
  number       = {37},
  pages        = {12773--12793},
  title        = {Kinetics of alpha hydrogen abstractions in thiols, sulfides and thiocarbonyl compounds},
  url          = {http://dx.doi.org/10.1039/C2CP41114H},
  volume       = {14},
  year         = {2012},
}

Chicago
Vandeputte, Aäron, Maarten Sabbe, Marie-Françoise Reyniers, and Guy Marin. 2012. “Kinetics of Alpha Hydrogen Abstractions in Thiols, Sulfides and Thiocarbonyl Compounds.” Physical Chemistry Chemical Physics 14 (37): 12773–12793.
APA
Vandeputte, Aäron, Sabbe, M., Reyniers, M.-F., & Marin, G. (2012). Kinetics of alpha hydrogen abstractions in thiols, sulfides and thiocarbonyl compounds. PHYSICAL CHEMISTRY CHEMICAL PHYSICS, 14(37), 12773–12793.
Vancouver
1.
Vandeputte A, Sabbe M, Reyniers M-F, Marin G. Kinetics of alpha hydrogen abstractions in thiols, sulfides and thiocarbonyl compounds. PHYSICAL CHEMISTRY CHEMICAL PHYSICS. 2012;14(37):12773–93.
MLA
Vandeputte, Aäron, Maarten Sabbe, Marie-Françoise Reyniers, et al. “Kinetics of Alpha Hydrogen Abstractions in Thiols, Sulfides and Thiocarbonyl Compounds.” PHYSICAL CHEMISTRY CHEMICAL PHYSICS 14.37 (2012): 12773–12793. Print.