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, C. T. O'Hara

Research output: Contribution to journalArticle

13 Citations (Scopus)

Abstract

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.

LanguageEnglish
Pages14424-14431
Number of pages8
JournalDalton Transactions
Volume43
Issue number38
Early online date24 Jun 2014
DOIs
Publication statusPublished - 14 Oct 2014

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Sodium
Diamines
Amides
Nuclear magnetic resonance spectroscopy
Byproducts
N,N,N',N'-tetramethylethylenediamine
Ions
Ligands
X rays
Chemical analysis

Keywords

  • sodium magnesiate
  • multinuclear NMR spectroscopy
  • X-ray crystallographic study

Cite this

Francos, J., Fleming, B. J., García-Álvarez, P., Kennedy, A. R., Reilly, K., Robertson, G. M., ... O'Hara, C. T. (2014). Complexity in seemingly simple sodium magnesiate systems. Dalton Transactions, 43(38), 14424-14431. https://doi.org/10.1039/c4dt00921e
Francos, J. ; Fleming, B. J. ; García-Álvarez, P. ; Kennedy, A. R. ; Reilly, K. ; Robertson, G. M. ; Robertson, S. D. ; O'Hara, C. T. / Complexity in seemingly simple sodium magnesiate systems. In: Dalton Transactions. 2014 ; Vol. 43, No. 38. pp. 14424-14431.
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Francos, J, Fleming, BJ, García-Álvarez, P, Kennedy, AR, Reilly, K, Robertson, GM, Robertson, SD & O'Hara, CT 2014, 'Complexity in seemingly simple sodium magnesiate systems' Dalton Transactions, vol. 43, no. 38, pp. 14424-14431. https://doi.org/10.1039/c4dt00921e

Complexity in seemingly simple sodium magnesiate systems. / Francos, J.; Fleming, B. J.; García-Álvarez, P.; Kennedy, A. R.; Reilly, K.; Robertson, G. M.; Robertson, S. D.; O'Hara, C. T.

In: Dalton Transactions, Vol. 43, No. 38, 14.10.2014, p. 14424-14431.

Research output: Contribution to journalArticle

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AU - Francos, J.

AU - Fleming, B. J.

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Francos J, Fleming BJ, García-Álvarez P, Kennedy AR, Reilly K, Robertson GM et al. Complexity in seemingly simple sodium magnesiate systems. Dalton Transactions. 2014 Oct 14;43(38):14424-14431. https://doi.org/10.1039/c4dt00921e