Intra- and intermolecular reactions of aromatic radical cations: an account of mechanistic concepts and methods in mass spectrometry

Grützmacher H-F (1993)
Organic Mass Spectrometry 28(12): 1375-1387.

Download
OA
Journal Article | Published | English
Abstract
Investigations in the authors's laboratory in Bielefeld and elsewhere on the mechanism of the intramolecular and intermolecular aromatic substitution via radical cations are reviewed with the aim of presenting an example for the development of mass spectrometric methods and concepts for the study of the mechanisms of gaseous ionic reactions. An intramolecular aromatic substitution resulting in the loss of a hydrogen or a substituent from an aromatic ring of the molecule ions by the attack of a nucleophilic heteroatom in the side-chain was first observed in the normal electron impact (EI) mass spectra and was studied by substituent effects on ion abundance, ionization energy and appearance energy. This led to the construction of a two-step mechanism of the intramolecular aromatic substitution with a rate-determining first addition step. Subsequently, this fragmentation reaction was studied for a series of systems by tandem mass spectrometry, confirming the two-step mechanism and yielding an excellent insight into the dynamics of the substitution process. The bimolecular variety of the nucleophilic aromatic substitution via radical cations was investigated recently by Fourier transform ion cyclotron resonance spectrometry. The results for a series of halogenated benzenes and NH 3, CH 3NH 2 and (CH 3) 2NH as the nucleophile corroborate the conclusions drawn from the study of unimolecular reaction mechanisms. It is shown that in all cases the formation and further reaction of the addition intermediate play a crucial role. This can be perceived by the application of the configuration mixing reactivity model to the addition reaction, and by the concept of classical and distonic radical cations. This review on a specific reaction mechanism shows clearly the excellent techniques and methods which the developments in mass spectrometry have provided for a detailed study of the mechanisms of ionic reactions in the gas phase.
Publishing Year
ISSN
eISSN
PUB-ID

Cite this

Grützmacher H-F. Intra- and intermolecular reactions of aromatic radical cations: an account of mechanistic concepts and methods in mass spectrometry. Organic Mass Spectrometry. 1993;28(12):1375-1387.
Grützmacher, H. - F. (1993). Intra- and intermolecular reactions of aromatic radical cations: an account of mechanistic concepts and methods in mass spectrometry. Organic Mass Spectrometry, 28(12), 1375-1387.
Grützmacher, H. - F. (1993). Intra- and intermolecular reactions of aromatic radical cations: an account of mechanistic concepts and methods in mass spectrometry. Organic Mass Spectrometry 28, 1375-1387.
Grützmacher, H.-F., 1993. Intra- and intermolecular reactions of aromatic radical cations: an account of mechanistic concepts and methods in mass spectrometry. Organic Mass Spectrometry, 28(12), p 1375-1387.
H.-F. Grützmacher, “Intra- and intermolecular reactions of aromatic radical cations: an account of mechanistic concepts and methods in mass spectrometry”, Organic Mass Spectrometry, vol. 28, 1993, pp. 1375-1387.
Grützmacher, H.-F.: Intra- and intermolecular reactions of aromatic radical cations: an account of mechanistic concepts and methods in mass spectrometry. Organic Mass Spectrometry. 28, 1375-1387 (1993).
Grützmacher, Hans-Friedrich. “Intra- and intermolecular reactions of aromatic radical cations: an account of mechanistic concepts and methods in mass spectrometry”. Organic Mass Spectrometry 28.12 (1993): 1375-1387.
Main File(s)
File Name
Access Level
OA Open Access

This data publication is cited in the following publications:
This publication cites the following data publications:

Export

0 Marked Publications

Open Data PUB

Web of Science

View record in Web of Science®

Search this title in

Google Scholar