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Synthesis of a stable adduct of dialane(4) (Al2H4) via hydrogenation of a magnesium(I) dimer

Nature Chemistry volume 2, pages 865–869 (2010)Cite this article

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Abstract

The desorption of dihydrogen from magnesium(II) hydride, MgH2 (containing 7.6 wt% H), is reversible. MgH2 therefore holds promise as a hydrogen storage material in devices powered by fuel cells. We believed that dimeric magnesium(I) dimers (LMgMgL, L = β-diketiminate) could find use as soluble models to aid the study of the mechanisms and/or kinetics of the hydrogenation of magnesium and its alloys. Here, we show that LMgMgL can be readily hydrogenated to yield LMg(µ-H)2MgL by treatment with aluminium(III) hydride complexes. In one case, hydrogenation was reversed by treating LMg(µ-H)2MgL with potassium metal. The hydrogenation by-products are the first thermally stable, neutral aluminium(II) hydride complexes to be produced, one of which, [{(IPr)(H)2Al}2] (IPr = :C[{(C6H3-i-Pr2-2,6)NCH}2]), is an N-heterocyclic carbene adduct of the elusive parent dialane(4) (Al2H4). A computational analysis of this compound is presented.

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Figure 1: Reaction scheme showing the transfer of hydrogen between aluminium(III) and magnesium(I) complexes.
Figure 2: Molecular structure of 3.
Figure 3: Molecular structures of 4 and 13.

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  • 13 October 2010

    In the HTML version of this Article originally published, the e-mail addresses for the corresponding authors were assigned incorrectly. This has now been corrected.

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Acknowledgements

The research was supported by the Australian Research Council (fellowships for C.J. and A.S.) and the Deutsche Forschungsgemeinschaft (grant no. FR641/25-1 to G.F.). The EPSRC is also thanked for access to the UK National Mass Spectrometry Facility.

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Authors and Affiliations

  1. School of Chemistry, Monash University, Melbourne, PO Box 23, Victoria, 3800, Australia

    Simon J. Bonyhady, David Collis, Cameron Jones & Andreas Stasch

  2. Fachbereich Chemie, Philipps-Universität Marburg, Marburg, 35032, Germany

    Gernot Frenking & Nicole Holzmann

Authors
  1. Simon J. Bonyhady
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  2. David Collis
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  3. Gernot Frenking
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  4. Nicole Holzmann
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  5. Cameron Jones
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  6. Andreas Stasch
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Contributions

Author listing order in the title is alphabetical. C.J. and A.S. conceived and designed the experiments. S.J.B., D.C. and A.S. performed the experiments. G.F. and N.H. carried out the computational studies. S.J.B., D.C., G.F., N.H., C.J. and A.S. analysed the data. C.J., A.S. and G.F. co-wrote the paper.

Corresponding authors

Correspondence to Gernot Frenking, Cameron Jones or Andreas Stasch.

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The authors declare no competing financial interests.

Supplementary information

Supplementary information

Supplementary information (PDF 1015 kb)

Supplementary information

Crystallographic data for compound 3 (CIF 15 kb)

Supplementary information

Crystallographic data for compound 4 (CIF 18 kb)

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Crystallographic data for compound 5 (CIF 21 kb)

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Crystallographic data for compound 9 (CIF 21 kb)

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Crystallographic data for compound 10·(cyclohexane) (CIF 22 kb)

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Crystallographic data for compound 11·(benzene)1.5 (CIF 64 kb)

Supplementary information

Crystallographic data for compound 12·(benzene)2 (CIF 25 kb)

Supplementary information

Crystallographic data for compound 13 (CIF 20 kb)

Supplementary information

Crystallographic data for compound 16 (CIF 27 kb)

Supplementary information

Crystallographic data for compound 17 (CIF 16 kb)

Supplementary information

Crystallographic data for compound 17·(benzene) (CIF 19 kb)

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Bonyhady, S., Collis, D., Frenking, G. et al. Synthesis of a stable adduct of dialane(4) (Al2H4) via hydrogenation of a magnesium(I) dimer. Nature Chem 2, 865–869 (2010). https://doi.org/10.1038/nchem.762

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