Solvent-free and TMEDA-solvated mixed alkali metal-magnesium tris-diisopropylamides

Hevia, E. and Kenley, F.R. and Kennedy, A.R. and Mulvey, R.E. and Rowlings, R.B. (2003) Solvent-free and TMEDA-solvated mixed alkali metal-magnesium tris-diisopropylamides. European Journal of Inorganic Chemistry, 2003 (18). pp. 3347-3353. ISSN 1434-1948 (http://dx.doi.org/10.1002/ejic.200300413)

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Abstract

A trio of heterobimetallic tris-diisopropylamides, the solvent-free potassium-magnesium amide [{KMg(NiPr2)(3)}(infinity)], its TMEDA solvate [KMg(NiPr2)(3).TMEDA] and the sodium congener [NaMg(NjPr(2))(3).TMEDA] has been synthesised by mixing the appropriate metal alkyl reagents with three molar equivalents of diisopropylamine in a hydrocarbon medium, to which, in the last two cases, TMEDA is added. All three amides have been successfully crystallographically characterised by X-ray diffraction studies. Representing the first pure s-block mixed-metal diisopropylamide free of solvent molecules or other stabilising anionic co-ligands, the first compound adopts an infinite spiral chain of ...K-(mu-N)(2)-Mg-N... links, the metal-N framework of which is supported by agostic K...C intra-dinuclear and inter-dinuclear contacts. The dinuclear tris-amido motif is maintained in both TMEDA complexes, the metal-N cores of which are essentially isostructural, but the presence of the chelating diamine blocks the propagating terminal site on the alkali metal and so gives rise to discrete molecular structures.

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