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A Synthetic and Theoretical Study of the Aggregation of Amidoaluminium Hydrides: Solid‐State Structure of the Trimethylamine Adduct [(Me 3 Si) 2 NA1(Cl)(H) · NMe 3 ]
Author(s) -
Gardiner Michael G.,
Koutsantonis George A.,
Lawrence Stacey M.,
Lee FuChin,
Raston Colin L.
Publication year - 1996
Publication title -
chemische berichte
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.667
H-Index - 136
eISSN - 1099-0682
pISSN - 0009-2940
DOI - 10.1002/cber.19961290511
Subject(s) - chemistry , adduct , trimethylsilyl , lewis acids and bases , trimethylamine , crystal structure , amine gas treating , hydride , crystallography , monomer , ab initio , stereochemistry , medicinal chemistry , catalysis , hydrogen , organic chemistry , polymer
Abstract The amidoaluminium hydride complexes [(Me 3 Si) 2 NA1(X)(H) · NMe 3 ], X = H ( 1 ), Cl ( 2 ), were prepared by the metallation of bis(trimethylsilyl)amine by Al(X)(H) 2 · NMe 3 (X = H and Cl). The molecular structure of 2 as a monomeric Lewis base adduct with four‐coordinate aluminium centres and terminal amido groups was confirmed by X‐ray crystal structure determination. We also find that bis(trimethylsilyl)amine forms a thermally stable adduct of alane, (Me 3 Si) 2 N(H) · AlH 3 ( 3 ). Ab initio molecular orbital calculations on the possible products arising from these reactions yielding 1 and 2 revealed that the amido‐bridged species, {(μ‐H 2 N)Al(X)H} 2 (X = H and Cl), are favoured over nitrogen donor Lewis base adduct formation, H 2 NAl(X)(H) · NH 3 (X = H and Cl), and then chloro‐bridged, {H 2 NAl(μ‐X)(H)} 2 , (X = Cl only), and hydrido‐bridged species, {H 2 NAl(X)(μ‐H)} 2 (X = H and Cl).