Molecular manipulations of a utility nitrogen-heterocyclic carbene by sodium magnesiate complexes and transmetallation chemistry with gold complexes

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Hevia, Eva and Hernán-Gómez, Alberto and Uzelac, Marina and Baillie, Sharon and Armstrong, David and Kennedy, Alan and Fuentes, Maria Ángeles (2018) Molecular manipulations of a utility nitrogen-heterocyclic carbene by sodium magnesiate complexes and transmetallation chemistry with gold complexes. Chemistry - A European Journal. ISSN 1521-3765 (https://doi.org/10.1002/chem.201802008)

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Abstract

Expanding the scope and applications of anionic N‐heterocyclic carbenes (NCHs), a novel series of magnesium NHC complexes is reported using a mixed‐sodium‐magnesium approach. Sequential reactivity of classical imidazol‐2‐ylidene carbene IPr with NaR and MgR2 (R= CH2SiMe3) affords [(THF)3Na(μ‐IPr─)MgR2(THF)] (2) [IPr─ = :C{[N(2,6‐iPr2C6H3)]2CHC] containing an anionic NHC ligand, whereas surprisingly sodium magnesiate [NaMgR3] fails to deprotonate IPr affording instead the redistribution coordination adduct [IPr2Na2MgR4] (1). Compound 2 undergoes selective C2‐methylation when treated with MeOTf furnishing novel abnormal NHC complex [{aIPrMeMgR2}2] (3). Dissolving 3 in THF led to the dissociation of this complex into MgR2 and aIPrMe with the latter isomerizing to the olefinic NHC IPr=CH2. The ability of 2 and 3 to transfer their anionic and abnormal NHC ligands respectively to Au(I) metal fragments has been investigated allowing the isolation and structural characterization of [RAu(μ‐IPr─)MgR(THF)2] (4) and [aIPrMeAuR] (5) respectively. In both cases transfer of an alkyl R group is observed. However while 3 can also transfer its abnormal NHC ligand to give 5, in 4 the anionic NHC still remains coordinated to Mg via its C4 position, whereas the {AuR} fragment occupies the C2 position previously filled by a donor‐solvated {Na(THF)3}+ cation.

ORCID iDs

Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506, Hernán-Gómez, Alberto ORCID logoORCID: https://orcid.org/0000-0001-8150-7249, Uzelac, Marina ORCID logoORCID: https://orcid.org/0000-0002-5060-7017, Baillie, Sharon, Armstrong, David, Kennedy, Alan ORCID logoORCID: https://orcid.org/0000-0003-3652-6015 and Fuentes, Maria Ángeles ORCID logoORCID: https://orcid.org/0000-0002-9095-9391;
  • Item type:Article
    ID code:64273
    Dates:
    Date
    Event
    11 May 2018
    Published
    11 May 2018
    Published Online
    9 May 2018
    Accepted
    Notes:This is the peer reviewed version of the following article: Hevia, E, Hernán-Gómez, A, Uzelac, M, Baillie, S, Armstrong, D, Kennedy, A & Fuentes, MÁ 2018, 'Molecular manipulations of a utility IPr nitrogen-heterocyclic carbene by sodium magnesiate complexes and transmetallation chemistry with gold complexes' Chemistry - A European Journal, which has been published in final form at https://doi.org/ 10.1002/chem.201802008. This article may be used for non-commercial purposes in accordance with Wiley Terms and Conditions for Use of Self-Archived Versions.
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:06 Jun 2018 13:33
    Last modified:17 Dec 2024 14:02
    Related URLs:
    URI:https://strathprints.strath.ac.uk/id/eprint/64273
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