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Issue 38, 2014
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Complexity in seemingly simple sodium magnesiate systems

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A systematic study both in the solid- and solution-state, was carried out for a series of sodium magnesiates containing the utility amide ligand 1,1,1,3,3,3-hexamethyldisilazide (HMDS). The first complex considered is the donor-free bisamido monoalkyl polymeric complex [Na(μ-HMDS)2Mg(nBu)]1. The reactivity of 1 with common tertiary bidentate donors including N,N,N′,N′-tetramethylethylenediamine (TMEDA) or its chiral relative (1R,2R)-tetramethylcyclohexyldiamine [(R,R)-TMCDA] is detailed. Surprisingly, the products of these reactions are not simple diamine adducts but are solvent separated sodium magnesiate systems [(TMEDA)2·Na]+[Mg(HMDS)3]2 and [{(R,R)-TMCDA}2·Na]+[Mg(HMDS)3]3. By concentrating on the likely equilibria which may give rise to formation of 2, a potential intermediate complexed ion pair [{(TMEDA)2·Na}(μ-nBu)Mg(HMDS)2] 4 was isolated. Additionally, the novel “inverse magnesiates” [{Na(μ-HMDS)}2Mg(μ-nBu)2·(TMEDA)]5 and [{Na(μ-HMDS)}2Mg(μ-nBu)2·{(R,R)-TMCDA}]6, were obtained by reacting solutions of composition “NaMg(HMDS)(nBu)2” (a likely by-product in the formation of 2 from 1), with TMEDA or (R,R)-TMCDA. The structure and nature of these bimetallic complexes have been determined using a combination of X-ray crystallographic studies and multinuclear NMR spectroscopy.

Graphical abstract: Complexity in seemingly simple sodium magnesiate systems

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The article was received on 28 Mar 2014, accepted on 24 Jun 2014 and first published on 24 Jun 2014

Article type: Paper
DOI: 10.1039/C4DT00921E
Citation: Dalton Trans., 2014,43, 14424-14431
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    Complexity in seemingly simple sodium magnesiate systems

    J. Francos, B. J. Fleming, P. García-Álvarez, A. R. Kennedy, K. Reilly, G. M. Robertson, S. D. Robertson and C. T. O'Hara, Dalton Trans., 2014, 43, 14424
    DOI: 10.1039/C4DT00921E

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