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A μ4-oxide-containing a dimeric variant of a sodium dialkyl(amido)zincate reagent
Liam Balloch1, Alan R Kennedy, Robert E Mulvey
1Department of Pure and Applied Chemistry, WestCHEM, University of Strathclyde, 295 Cathedral Street, Glasgow G1 1XL, Scotland.
Abstract:
Post-metallation derivatives of the sodium dialkyl(amido)zincate reagent (TMEDA)Na(μ-TMP)Zn((t)Bu)(2) (TMEDA is N,N,N',N'-tetramethylethylenediamine and TMP is 2,2,6,6-tetramethylpiperidide) have been of structural interest due to the insight they give into aromatic metallation mechanisms. Here, the aromatic substrate is formally replaced with [ZnO](2) to give tetra-tert-butyldi-μ(4)-oxido-bis(tetramethylethylenediamine-κ(2)N,N')bis(μ(2)-2,2,6,6-tetramethylpiperidin-1-ido-κ(2)N:N)disodiumtetrazinc hexane 0.59-solvate, [Na(2)Zn(4)(C(4)H(9))(4)(C(9)H(18)N)(2)O(2)(C(6)H(16)N(2))(2)]·0.59C(6)H(14). The crystallographically centrosymmetric complex retains many of the structural features of its parent monomer but has an unusual dimeric structure, with a central planar Zn-O-Zn-O ring joined to two orthogonal near-planar Zn-O-Na-N rings through the distorted tetrahedral geometries of the oxide ions.
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The nitrous acid is unstable. Hence, it is formed in situ from a solution of sodium nitrite and cold aqueous acids such as hydrochloric or sulfuric acid. In an acidic solution, the –OH group of nitrous acid undergoes protonation to give oxonium ion, followed by water loss...
