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Multiple deprotonation of primary aromatic diamines by LiAlH 4

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

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Bibliographic Details
Published in:Dalton transactions : an international journal of inorganic chemistry 2015, Vol.44 (9), p.4141-4147
Main Authors: Less, Robert J., Allen, Lucy K., Steiner, Alexander, Wright, Dominic S.
Format: Article
Language:English
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Summary:Reaction of LiAlH 4 with 1,2-phenylenediamine ( 1 H 4 ) in THF results in formation of the metallocyclic amido-/imido complex [{Al( 1 H 2 )} 2 {Al( 1 H) 2 } 2 ][Li(THF) 2 ] 4 ( 3 ), while in the presence of various Lewis base ligands 1,8-diaminonaphthalene ( 2 H 4 ) gives the amido-(‘ate’) complexes [Al( 2 H 2 ) 2 ] − [Li(LL′)] + [L = THF, L′ = PMDETA ( N , N , N ′, N ′, N ′′-pentamethyldiethylenetriamine) ( 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( 1 H 2 )} 2 {Al( 1 H) 2 } 2 ] 4− of 3 .
ISSN:1477-9226
1477-9234
DOI:10.1039/C4DT03802A