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Hydrocarbon Soluble Alkali‐Metal‐Aluminium Hydride Surrog[ATES]
Author(s) -
Banerjee Sumanta,
Macdonald Peter A.,
Orr Samantha A.,
Kennedy Alan R.,
Teijlingen Alexander,
Robertson Stuart D.,
Tuttle Tell,
Mulvey Robert E.
Publication year - 2022
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/chem.202201085
Subject(s) - alkali metal , chemistry , aluminate , hydride , bimetallic strip , lithium (medication) , inorganic chemistry , metal , covalent bond , reactivity (psychology) , crystallography , organic chemistry , materials science , metallurgy , medicine , alternative medicine , pathology , cement , endocrinology
A series of group 1 hydrocarbon‐soluble donor free aluminates [AM( t BuDHP)(TMP)Al( i Bu) 2 ] (AM=Li, Na, K, Rb) have been synthesised by combining an alkali metal dihydropyridyl unit [(2‐ t BuC 5 H 5 N)AM)] containing a surrogate hydride (sp 3 C−H) with [( i Bu) 2 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( t BuDHP)(TMP)Al( i Bu) 2 ] and [(TMEDA)Na( t BuDHP)(TMP)Al( i Bu) 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].