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Hydrocarbon Soluble Alkali-Metal-Aluminium Hydride Surrog[ATES] |
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| Authors: | Dr. Sumanta Banerjee Peter A. Macdonald Dr. Samantha A. Orr Dr. Alan R. Kennedy Alexander van Teijlingen Dr. Stuart D. Robertson Prof. Tell Tuttle Prof. Robert E. Mulvey |
| Affiliation: | 1. WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL UK Contribution: Data curation (lead), Investigation (equal), Writing - original draft (equal);2. WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL UK Contribution: Methodology (supporting);3. WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL UK;4. WestCHEM, Department of Pure and Applied Chemistry, University of Strathclyde, Glasgow, G1 1XL UK Contribution: Software (equal), Writing - review & editing (supporting) |
| Abstract: | A series of group 1 hydrocarbon-soluble donor free aluminates [AM(tBuDHP)(TMP)Al(iBu)2] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2-tBuC5H5N)AM)] containing a surrogate hydride (sp3 C−H) with [(iBu)2Al(TMP)]. These aluminates have been characterised by X-ray crystallography and NMR spectroscopy. While the lithium aluminate forms a monomer, the heavier alkali metal aluminates exist as polymeric chains propagated by non-covalent interactions between the alkali metal cations and the alkyldihydropyridyl units. Solvates [(THF)Li(tBuDHP)(TMP)Al(iBu)2] and [(TMEDA)Na(tBuDHP)(TMP)Al(iBu)2] have also been crystallographically characterised. Theoretical calculations show how the dispersion forces tend to increase on moving from Li to Rb, as opposed to the electrostatic forces of stabilization, which are orders of magnitude more significant. Having unique structural features, these bimetallic compounds can be considered as starting points for exploring unique reactivity trends as alkali-metal-aluminium hydride surrog[ATES]. |
| Keywords: | alkali metal aluminates dihydropyridine heterobimetallic complexes hydride London dispersion forces |