Multiple deprotonation of primary aromatic diamines by LiAlH sub(4)

Reaction of LiAlH sub(4) with 1,2-phenylenediamine (1H sub(4)) in THF results in formation of the metallocyclic amido-/imido complex [{Al(1H sub(2))} sub(2){Al(1H) sub(2)} sub(2)][Li(THF) sub(2)] sub(4) (3), while in the presence of various Lewis base ligands 1,8-diaminonaphthalene (2H sub(4)) gives...

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2015-02, Vol.44 (9), p.4141-4147
Main Authors: Less, Robert J, Allen, Lucy K, Steiner, Alexander, Wright, Dominic S
Format: Article
Language:English
Subjects:
Diamines
Formations
Lewis base
Ligands
Pathways
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Summary:Reaction of LiAlH sub(4) with 1,2-phenylenediamine (1H sub(4)) in THF results in formation of the metallocyclic amido-/imido complex [{Al(1H sub(2))} sub(2){Al(1H) sub(2)} sub(2)][Li(THF) sub(2)] sub(4) (3), while in the presence of various Lewis base ligands 1,8-diaminonaphthalene (2H sub(4)) gives the amido-('ate') complexes [Al(2H sub(2)) sub(2)] super(-)[Li(LL')] super(+) [L = THF, L' = PMDETA (N,N,N',N',N''-pentame thyldiethylenetriamine) (4); L = L' = TMEDA (N,N,N',N'-tetramethylethylenediamine) (5)]. The latter complexes provide evidence of intermediates in the proposed reaction pathway for formation of the cyclic framework of the tetraanion [{Al(1H sub(2))} sub(2){Al(1H) sub(2)} sub(2)] super(4-) of 3.
ISSN:1477-9226
1477-9234
DOI:10.1039/c4dt03802a