Organozinc pivalate reagents : segregation, solubility, stabilisation and structural insights

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Hernán-Gómez, Alberto and Herd, Emma and Hevia, Eva and Kennedy, Alan R. and Knochel, Paul and Koszinowski, Konrad and Manolikakes, Sophia M. and Mulvey, Robert E. and Schnegelsberg, Christoph (2014) Organozinc pivalate reagents : segregation, solubility, stabilisation and structural insights. Angewandte Chemie International Edition, 53 (10). 2706–2710. ISSN 1521-3773 (https://doi.org/10.1002/anie.201309841)

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Abstract

The pivalates RZnOPiv⋅Mg(OPiv)X⋅n LiCl (OPiv=pivalate; R=aryl; X=Cl, Br, I) stand out amongst salt-supported organometallic reagents, because apart from their effectiveness in Negishi cross-coupling reactions, they show more resistance to attack by moist air than conventional organometallic compounds. Herein a combination of synthesis, coupling applications, X-ray crystallographic studies, NMR (including DOSY) studies, and ESI mass spectrometric studies provide details of these pivalate reagents in their own right. A p-tolyl case system shows that in [D8]THF solution these reagents exist as separated Me(p-C6H4)ZnCl and Mg(OPiv)2 species. Air exposure tests and X-ray crystallographic studies indicate that Mg(OPiv)2 enhances the air stability of aryl zinc species by sequestering H2O contaminants. Coupling reactions of Me(p-C6H4)ZnX (where X=different salts) with 4-bromoanisole highlight the importance of the presence of Mg(OPiv)2. Insight into the role of LiCl in these multicomponent mixtures is provided by the molecular structure of [(THF)2Li2(Cl)2(OPiv)2Zn].

ORCID iDs

Hernán-Gómez, Alberto ORCID logoORCID: https://orcid.org/0000-0001-8150-7249, Herd, Emma, Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Knochel, Paul, Koszinowski, Konrad, Manolikakes, Sophia M., Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564 and Schnegelsberg, Christoph;
  • Item type:Article
    ID code:47090
    Dates:
    Date
    Event
    3 March 2014
    Published
    31 January 2014
    Published Online
    Notes:This is the peer reviewed version of the following article: Hernan-Gomez, A., Herd, E., Hevia, E., Kennedy, A., Knochel, P., Koszinowski, K., ... Mulvey, R. (2014). Organozinc pivalate reagents: segregation, solubility, stabilisation and structural insights. Angewandte Chemie International Edition, 53, 2706–2710, which has been published in final form at http://dx.doi.org/10.1002/anie.201309841. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Self-Archiving.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:04 Mar 2014 10:23
    Last modified:12 Dec 2024 02:53
    URI:https://strathprints.strath.ac.uk/id/eprint/47090
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