Structural diversity in alkali metal and alkali metal magnesiate chemistry of the bulky 2,6-diisopropyl-N-(trimethylsilyl)anilino ligand

Fuentes, M. Angeles and Zabala, Andoni and Kennedy, Alan R. and Mulvey, Robert E. (2016) Structural diversity in alkali metal and alkali metal magnesiate chemistry of the bulky 2,6-diisopropyl-N-(trimethylsilyl)anilino ligand. Chemistry - A European Journal, 22. pp. 14968-14978. ISSN 0947-6539

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    Abstract

    Bulky amido ligands are precious in s-block chemistry since they can implant complementary strong basic and weak nucleophilic properties within compounds. Recent work has shown the pivotal importance of the base structure with enhancement of basicity and extraordinary regioselectivities possible for cyclic alkali metal magnesiates containing mixed n-butyl/amido ligand sets. This work advances alkali metal and alkali metal magnesiate chemistry of the bulky aryl-silyl amido ligand [N(SiMe3)(Dipp)] (Dipp = 2,6-iPr2-C6H3). Infinite chain structures of the parent sodium and potassium amides are disclosed, adding to the few known crystallographically characterised unsolvated s-block metal amides. Solvation by PMDETA or TMEDA gives molecular variants of the lithium and sodium amides; whereas for potassium, PMDETA gives a molecular structure but TMEDA affords a novel, hemi-solvated infinite chain. Crystal structures of the first magnesiate examples of this amide in [MMg{N(SiMe3)(Dipp)}2(μ-nBu)]∞ (M = Na or K), are also revealed though these breakdown to their homometallic components in donor solvent as revealed through NMR and DOSY studies.

    ORCID iDs

    Fuentes, M. Angeles ORCID logoORCID: https://orcid.org/0000-0002-9095-9391, Zabala, Andoni, Kennedy, Alan R. ORCID logoORCID: https://orcid.org/0000-0003-3652-6015 and Mulvey, Robert E. ORCID logoORCID: https://orcid.org/0000-0002-1015-2564;
    • Item type:Article
      ID code:57016
      Dates:
      Date
      Event
      30 August 2016
      Published
      7 July 2016
      Accepted
      Keywords:alkali metal, amides, bases, crystal structure, magnesiates, metallation, Chemistry, Chemistry(all)
      Subjects:Science > Chemistry
      Department:Faculty of Science > Pure and Applied Chemistry
      Depositing user: Pure Administrator
      Date deposited:21 Jul 2016 09:24
      Last modified:09 Jun 2021 00:39
      URI:https://strathprints.strath.ac.uk/id/eprint/57016
    CORE (COnnecting REpositories)