Heavy alkali metal manganate complexes : synthesis, structures and solvent-induced dissociation effects

Ballmann, Gerd M. and Gentner, Thomas X. and Kennedy, Alan R. and Hevia, Eva and Mulvey, Robert E. (2022) Heavy alkali metal manganate complexes : synthesis, structures and solvent-induced dissociation effects. Chemistry - A European Journal, 28 (55). e202201716. ISSN 1521-3765 (https://doi.org/10.1002/chem.202201716)

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Abstract

Rare examples of heavier alkali metal manganates [{(AM)Mn(CH 2SiMe 3)(N ‘Ar) 2} ∞] (AM=K, Rb, or Cs) [N ‘Ar=N(SiMe 3)(Dipp), where Dipp=2,6-iPr 2-C 6H 3] have been synthesised with the Rb and Cs examples crystallographically characterised. These heaviest manganates crystallise as polymeric zig-zag chains propagated by AM⋅⋅⋅π-arene interactions. Key to their preparation is to avoid Lewis base donor solvents. In contrast, using multidentate nitrogen donors encourages ligand scrambling leading to redistribution of these bimetallic manganate compounds into their corresponding homometallic species as witnessed for the complete Li - Cs series. Adding to the few known crystallographically characterised unsolvated and solvated rubidium and caesium s-block metal amides, six new derivatives ([{AM(N ‘Ar)} ∞], [{AM(N ‘Ar)⋅TMEDA} ∞], and [{AM(N ‘Ar)⋅PMDETA} ∞] where AM=Rb or Cs) have been structurally authenticated. Utilising monodentate diethyl ether as a donor, it was also possible to isolate and crystallographically characterise sodium manganate [(Et 2O) 2Na( nBu)Mn[(N ‘Ar) 2], a monomeric, dinuclear structure prevented from aggregating by two blocking ether ligands bound to sodium.

ORCID iDs

Ballmann, Gerd M., Gentner, Thomas X., Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015, Hevia, Eva ORCID logoORCID: https://orcid.org/0000-0002-3998-7506 and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
  • Item type:Article
    ID code:81386
    Dates:
    Date
    Event
    4 October 2022
    Published
    1 July 2022
    Published Online
    30 June 2022
    Accepted
    Subjects:Science > Chemistry
    Department:Faculty of Science > Pure and Applied Chemistry
    Depositing user: Pure Administrator
    Date deposited:07 Jul 2022 10:30
    Last modified:11 Nov 2024 13:32
    URI:https://strathprints.strath.ac.uk/id/eprint/81386
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