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 (https://doi.org/10.1002/chem.201602683)

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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.

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