Nair, Nanditha G. and Mendoza-Cortes, Jose L. and Abrol, Ravinder and Goddard, William A., III and Reddy, V. Prakash (2013) 1,3-Sigmatropic fluorine migration to boron in McLafferty type of rearrangements: Observation of tetrafluorobenzyne radical cation and trifluorobenzyne cation by CID-mass spectrometry. Journal of Organometallic Chemistry, 747 . pp. 133-139. ISSN 0022-328X. doi:10.1016/j.jorganchem.2013.06.006. https://resolver.caltech.edu/CaltechAUTHORS:20131202-091613488
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Abstract
The electron-impact mass spectra of the tris(pentafluorophenyl)boroxine (1) and triphenylboroxine (2) were analyzed to probe the McLafferty type of rearrangements involving 1,3-fluorine or 1,3-hydrogen migrations to boron from the adjacent aromatic rings. 1,3-Sigmatropic fluorine migration leading to the McLafferty rearrangement of 1 results in the formation of the tetrafluorobenzyne radical cation (1c), whereas the similar rearrangement involving 1,3-hydrogen rearrangement is not observed for the nonfluorinated analog 2. The DFT calculations show that the activation barrier for the 1,3-fluorine migration in 1 is significantly lower than that for the 1,3-hydrogen migration in 2 (ΔΔG^‡ ∼33 kcal/mol), which is in accordance with the observed 1,3-fluorine migration for the fluorinated boroxine and the lack of such rearrangement for the nonfluorinated boroxine. The 1:1 stoichiometry of the fluoride anion with 1 has also been demonstrated by high resolution electrospray ionization time-of-flight mass spectrometry.
| Item Type: | Article | |||||||||
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| Additional Information: | © 2013 Elsevier B.V. Received 21 February 2013. Received in revised form. 1 June 2013. Accepted 6 June 2013. We gratefully acknowledge Mona Shahgholi at Caltech mass spectroscopic facilities for EI/HRMS spectra. One of us (NN) thanks Dr. Simon Jones and Professor Robert H. Grubbs for their encouragement. | |||||||||
| Subject Keywords: | Boroxine; Benzyne radical cation; Benzyne cation; Sigmatropic rearrangement; DFT calculations | |||||||||
| DOI: | 10.1016/j.jorganchem.2013.06.006 | |||||||||
| Record Number: | CaltechAUTHORS:20131202-091613488 | |||||||||
| Persistent URL: | https://resolver.caltech.edu/CaltechAUTHORS:20131202-091613488 | |||||||||
| Official Citation: | Nanditha G. Nair, Jose L. Mendoza-Cortes, Ravinder Abrol, William A. Goddard III, V. Prakash Reddy, 1,3-Sigmatropic fluorine migration to boron in McLafferty type of rearrangements: Observation of tetrafluorobenzyne radical cation and trifluorobenzyne cation by CID-mass spectrometry, Journal of Organometallic Chemistry, Volume 747, 1 December 2013, Pages 133-139, ISSN 0022-328X, http://dx.doi.org/10.1016/j.jorganchem.2013.06.006. | |||||||||
| Usage Policy: | No commercial reproduction, distribution, display or performance rights in this work are provided. | |||||||||
| ID Code: | 42764 | |||||||||
| Collection: | CaltechAUTHORS | |||||||||
| Deposited By: | Ruth Sustaita | |||||||||
| Deposited On: | 02 Dec 2013 17:34 | |||||||||
| Last Modified: | 10 Nov 2021 16:28 |
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