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Hydrocarbon Soluble Alkali-Metal-Aluminium Hydride Surrog[ATES].

Authors :: Banerjee S
Macdonald PA
Orr SA
Kennedy AR
van Teijlingen A
Robertson SD
Tuttle T
Mulvey RE
Source :: Chemistry (Weinheim an der Bergstrasse, Germany) [Chemistry] 2022 Oct 04; Vol. 28 (55), pp. e202201085. Date of Electronic Publication: 2022 Aug 11.
Publication Year :: 2022
Abstract: A series of group 1 hydrocarbon-soluble donor free aluminates [AM( <superscript>t</superscript> BuDHP)(TMP)Al( <superscript>i</superscript> Bu) <subscript>2</subscript> ] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2- <superscript>t</superscript> BuC <subscript>5</subscript> H <subscript>5</subscript> N)AM)] containing a surrogate hydride (sp <superscript>3</superscript> C-H) with [( <superscript>i</superscript> Bu) <subscript>2</subscript> Al(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( <superscript>t</superscript> BuDHP)(TMP)Al( <superscript>i</superscript> Bu) <subscript>2</subscript> ] and [(TMEDA)Na( <superscript>t</superscript> BuDHP)(TMP)Al( <superscript>i</superscript> Bu) <subscript>2</subscript> ] 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].<br /> (© 2022 The Authors. Chemistry - A European Journal published by Wiley-VCH GmbH.)