Alkali-metal-mediated magnesiations of an N-heterocyclic carbene : normal, abnormal and "paranormal" reactivity in a single tritopic molecule

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Martínez-Martínez, Antonio J. and Fuentes, M. Ángeles and Hernán-Gõmez, Alberto and Hevia, Eva and Kennedy, Alan R. and Mulvey, Robert E. and O'Hara, Charles T. (2015) Alkali-metal-mediated magnesiations of an N-heterocyclic carbene : normal, abnormal and "paranormal" reactivity in a single tritopic molecule. Angewandte Chemie International Edition, 54 (47). pp. 14075-14079. ISSN 1521-3773 (https://doi.org/10.1002/anie.201507586)

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Abstract

Herein the sodium alkylmagnesium amide [Na4Mg2(TMP)6(nBu)2] (TMP=2,2,6,6-tetramethylpiperidide), a template base as its deprotonating action is dictated primarily by its 12 atom ring structure, is studied with the common N-heterocyclic carbene (NHC) IPr [1,3-bis(2,6-diisopropylphenyl)imidazol-2-ylidene]. Remarkably, magnesiation of IPr occurs at the para-position of an aryl substituent, sodiation occurs at the abnormal C4 position, and a dative bond occurs between normal C2 and sodium, all within a 20 atom ring structure accommodating two IPr2-. Studies with different K/Mg and Na/Mg bimetallic bases led to two other magnesiated NHC structures containing two or three IPr- monoanions bound to Mg through abnormal C4 sites. Synergistic in that magnesiation can only work through alkali-metal mediation, these reactions add magnesium to the small cartel of metals capable of directly metalating a NHC.

ORCID iDs

Martínez-Martínez, Antonio J., Fuentes, M. Ángeles, Hernán-Gõmez, Alberto ORCID logoORCID: https://orcid.org/0000-0001-8150-7249, Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and O'Hara, Charles T.;
  • Item type:Article
    ID code:54271
    Dates:
    Date
    Event
    16 November 2015
    Published
    29 September 2015
    Published Online
    10 September 2015
    Accepted
    Notes:This is the peer reviewed version of the following article: Martínez-Martínez, A. J., Fuentes, M. Á., Hernán-Gómez, A., Hevia, E., Kennedy, A. R., Mulvey, R. E. and O'Hara, C. T. (2015), Alkali-Metal-Mediated Magnesiations of an N-Heterocyclic Carbene: Normal, Abnormal, and “Paranormal” Reactivity in a Single Tritopic Molecule. Angew. Chem. Int. Ed., 54: 14075–14079, which has been published in final form at http://dx.doi.org/doi: 10.1002/anie.201507586. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
    Subjects:Science > Chemistry
    Department:University of Strathclyde > University of Strathclyde
    Depositing user: Pure Administrator
    Date deposited:11 Sep 2015 14:09
    Last modified:17 Dec 2024 01:14
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/54271
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