Does Addition of NO2 to Carbon-Centered Radicals Yield RONO or RNO2? An Investigation Using Distonic Radical Ions

Kirk, B. B., Trevitt, A. J., & Blanksby, S. J. (2013) Does Addition of NO2 to Carbon-Centered Radicals Yield RONO or RNO2? An Investigation Using Distonic Radical Ions. Journal of the American Society for Mass Spectrometry, 24(4), pp. 481-492.

View at publisher

Abstract

Nitrogen dioxide is used as a "radical scavenger" to probe the position of carbon-centered radicals within complex radical ions in the gas phase. As with analogous neutral radical reactions, this addition results in formation of an [M + NO2](+) adduct, but the structural identity of this species remains ambiguous. Specifically, the question remains: do such adducts have a nitro-(RNO2) or nitrosoxy-(RONO) moiety, or are both isomers present in the adduct population? In order to elucidate the products of such reactions, we have prepared and isolated three distonic phenyl radical cations and observed their reactions with nitrogen dioxide in the gas phase by ion-trap mass spectrometry. In each case, stabilized [M + NO2](+) adduct ions are observed and isolated. The structure of these adducts is probed by collision-induced dissociation and ultraviolet photodissociation action spectroscopy and a comparison made to the analogous spectra of authentic nitro-and nitrosoxy-benzenes. We demonstrate unequivocally that for the phenyl radical cations studied here, all stabilized [M + NO2](+) adducts are exclusively nitrobenzenes. Electronic structure calculations support these mass spectrometric observations and suggest that, under low-pressure conditions, the nitrosoxy-isomer is unlikely to be isolated from the reaction of an alkyl or aryl radical with NO2. The combined experimental and theoretical results lead to the prediction that stabilization of the nitrosoxy-isomer will only be possible for systems wherein the energy required for dissociation of the RO-NO bond (or other low energy fragmentation channels) rises close to, or above, the energy of the separated reactants.

Impact and interest:

1 citations in Scopus
Search Google Scholar™
2 citations in Web of Science®

Citation counts are sourced monthly from Scopus and Web of Science® citation databases.

These databases contain citations from different subsets of available publications and different time periods and thus the citation count from each is usually different. Some works are not in either database and no count is displayed. Scopus includes citations from articles published in 1996 onwards, and Web of Science® generally from 1980 onwards.

Citations counts from the Google Scholar™ indexing service can be viewed at the linked Google Scholar™ search.

Full-text downloads:

14 since deposited on 20 Mar 2014
4 in the past twelve months

Full-text downloads displays the total number of times this work’s files (e.g., a PDF) have been downloaded from QUT ePrints as well as the number of downloads in the previous 365 days. The count includes downloads for all files if a work has more than one.

ID Code: 68892
Item Type: Journal Article
Refereed: Yes
Additional URLs:
Keywords: Distonic radical ions, Ion-trap mass spectrometry, Ion-molecule, reactions, Photodissociation, Action spectroscopy, collision-induced dissociation, tandem mass-spectrometry, gas-phase, nitric-oxide, kinetics, decomposition, mechanism, trap, ionization, pathways, ARC
DOI: 10.1007/s13361-012-0549-x
ISSN: 1044-0305
Subjects: Australian and New Zealand Standard Research Classification > CHEMICAL SCIENCE (030000)
Divisions: Current > QUT Faculties and Divisions > Science & Engineering Faculty
Funding:
Copyright Owner: Springer
Deposited On: 20 Mar 2014 03:12
Last Modified: 18 Jan 2016 17:57

Export: EndNote | Dublin Core | BibTeX

Repository Staff Only: item control page