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Issue 20, 2020
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Reactivity and rotational spectra: the old concept of substitution effects

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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.

Graphical abstract: Reactivity and rotational spectra: the old concept of substitution effects

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Supplementary files

Article information


Submitted
28 Feb 2020
Accepted
25 Apr 2020
First published
11 May 2020

This article is Open Access

Phys. Chem. Chem. Phys., 2020,22, 11490-11497
Article type
Paper

Reactivity and rotational spectra: the old concept of substitution effects

S. Herbers, P. Buschmann, J. Wang, K. G. Lengsfeld, K. P. R. Nair and J. Grabow, Phys. Chem. Chem. Phys., 2020, 22, 11490
DOI: 10.1039/D0CP01145B

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