Details
| Original language | English |
|---|---|
| Pages (from-to) | 11490-11497 |
| Number of pages | 8 |
| Journal | Physical Chemistry Chemical Physics |
| Volume | 22 |
| Issue number | 20 |
| Early online date | 11 May 2020 |
| Publication status | Published - 28 May 2020 |
Abstract
The internal rotation of methyl groups and nuclear quadrupole moments of the halogens Cl, Br, I in o-halotoluenes cause complex spectral fine and hyperfine structures in rotational spectra arising from angular momentum coupling. Building on the existing data regarding o-fluorotoluene and o-chlorotoluene, the investigations of o-bromotoluene and o-iodotoluene allow for a complete analysis of the homologous series of o-halogenated toluenes. The trend in the methyl barriers to internal rotation rising with the size of the halogen can be rationalised by repulsion effects as predicted by MP2 calculations. Furthermore, the analysis of the observed quadrupole coupling serves as a quantitative intra-molecular probe, e.g. for the explanation of the relative reaction yields in the nitration of halotoluenes, related to the different π-bond character of the C-X bond depending on the position of substitution.
ASJC Scopus subject areas
- Physics and Astronomy(all)
- General Physics and Astronomy
- Chemistry(all)
- Physical and Theoretical Chemistry
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In: Physical Chemistry Chemical Physics, Vol. 22, No. 20, 28.05.2020, p. 11490-11497.
Research output: Contribution to journal › Article › Research › peer review
}
TY - JOUR
T1 - Reactivity and rotational spectra
T2 - The old concept of substitution effects
AU - Herbers, Sven
AU - Buschmann, Philipp
AU - Wang, Juan
AU - Lengsfeld, Kevin Gregor
AU - Nair, K. P.Rajappan
AU - Grabow, Jens Uwe
N1 - Funding Information: J. W. wants to thank the China Scholarships Council (CSC) for financial support. K. G. L. wants to thank the Fonds der Chemischen Industrie (FCI) for his fellowship. We want to acknowledge the financial support of the Land Niedersachsen, the Deutsche Forschungsgemeinschaft (DFG) and the support of the cluster system team at the Leibniz University IT services (LUIS) Hannover, Germany.
PY - 2020/5/28
Y1 - 2020/5/28
N2 - The internal rotation of methyl groups and nuclear quadrupole moments of the halogens Cl, Br, I in o-halotoluenes cause complex spectral fine and hyperfine structures in rotational spectra arising from angular momentum coupling. Building on the existing data regarding o-fluorotoluene and o-chlorotoluene, the investigations of o-bromotoluene and o-iodotoluene allow for a complete analysis of the homologous series of o-halogenated toluenes. The trend in the methyl barriers to internal rotation rising with the size of the halogen can be rationalised by repulsion effects as predicted by MP2 calculations. Furthermore, the analysis of the observed quadrupole coupling serves as a quantitative intra-molecular probe, e.g. for the explanation of the relative reaction yields in the nitration of halotoluenes, related to the different π-bond character of the C-X bond depending on the position of substitution.
AB - The internal rotation of methyl groups and nuclear quadrupole moments of the halogens Cl, Br, I in o-halotoluenes cause complex spectral fine and hyperfine structures in rotational spectra arising from angular momentum coupling. Building on the existing data regarding o-fluorotoluene and o-chlorotoluene, the investigations of o-bromotoluene and o-iodotoluene allow for a complete analysis of the homologous series of o-halogenated toluenes. The trend in the methyl barriers to internal rotation rising with the size of the halogen can be rationalised by repulsion effects as predicted by MP2 calculations. Furthermore, the analysis of the observed quadrupole coupling serves as a quantitative intra-molecular probe, e.g. for the explanation of the relative reaction yields in the nitration of halotoluenes, related to the different π-bond character of the C-X bond depending on the position of substitution.
UR - http://www.scopus.com/inward/record.url?scp=85085534978&partnerID=8YFLogxK
U2 - 10.1039/d0cp01145b
DO - 10.1039/d0cp01145b
M3 - Article
C2 - 32391831
AN - SCOPUS:85085534978
VL - 22
SP - 11490
EP - 11497
JO - Physical Chemistry Chemical Physics
JF - Physical Chemistry Chemical Physics
SN - 1463-9076
IS - 20
ER -