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1,3-Sigmatropic fluorine migration to boron in McLafferty type of rearrangements: Observation of tetrafluorobenzyne radical cation and trifluorobenzyne cation by CID-mass spectrometry

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
Related URLs:
URLURL TypeDescription
http://dx.doi.org/10.1016/j.jorganchem.2013.06.006DOIArticle
http://www.sciencedirect.com/science/article/pii/S0022328X13004464PublisherArticle
ORCID:
AuthorORCID
Abrol, Ravinder0000-0001-7333-6793
Goddard, William A., III0000-0003-0097-5716
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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