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    Sigma/pi Bonding Preferences of Solvated Alkali‐Metal Cations to Ditopic Arylmethyl Anions

    Rae, Annabel and Byrne, Keelan M. and Brown, Scott A. and Kennedy, Alan R. and Krämer, Tobias and Mulvey, Robert E. and Robertson, Stuart D. (2022) Sigma/pi Bonding Preferences of Solvated Alkali‐Metal Cations to Ditopic Arylmethyl Anions. Chemistry – A European Journal, 28 (18). pp. 1-17. ISSN 0947-6539

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    Arylmethyl anions allow alkali-metals to bind in a σ-fashion to the lateral carbanionic centre or a π-fashion to the aryl ring or in between these extremities, with the trend towards π bonding increasing on descending group 1. Here we review known alkali metal structures of diphenylmethane, fluorene, 2-benzylpyridine and 4-benzylpyridine. Next, we synthesise Li, Na, K monomers of these diarylmethyls using polydentate donors PMDETA or Me6TREN to remove competing oligomerizing interactions, studying the effect that two aromatic rings has on negative charge (de)localisation via NMR, X-ray crystallographic and DFT studies. Diphenylmethyl and fluorenyl anions maintain C(H)−M interactions regardless of alkali-metal, although the adjacent arene carbons engage in interactions with larger alkali-metals. Introducing a nitrogen atom into the ring (at the 2- or 4-position) encourages relocalisation of negative charge away from the deprotonated carbon and onto nitrogen. Phenyl(2-pyridyl)methyl moves from an enamide formation at one extremity (lithium) to an aza-allyl formation at the other extremity (potassium), while C- or N-coordination modes become energetically viable for Na and K phenyl(4-pyridyl)methyl complexes.

    Item Type: Article
    Keywords: Sigma; pi; Bonding; Preferences; Solvated; Alkali‐Metal; Cations; Ditopic Arylmethyl Anions;
    Academic Unit: Faculty of Science and Engineering > Chemistry
    Faculty of Science and Engineering > Research Institutes > Hamilton Institute
    Item ID: 18518
    Identification Number:
    Depositing User: Tobias Kraemer
    Date Deposited: 15 May 2024 10:28
    Journal or Publication Title: Chemistry – A European Journal
    Publisher: Wiley
    Refereed: Yes
    Use Licence: This item is available under a Creative Commons Attribution Non Commercial Share Alike Licence (CC BY-NC-SA). Details of this licence are available here

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