Anionic and Neutral Aluminum Bis(N,N'-di-tert-butylethylenediamide) Complexes: [Al{[N(t-Bu)CH2]2}2]- and [Al{[N(t-Bu)CH2]2}2]

Michael G. Gardiner, Colin L. Raston, Brian W. Skelton, Allan H. White

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Abstract

The reaction of the aluminum triamide [{HN(t-Bu)CH2CH2N-t-Bu}Al{N(t-Bu)CH2} 2 (1) with n-BuLi in hexane and diethyl ether gives the monomeric solvent-free lithium aluminum tetraamide [Li{N(t-Bu)CH2CH2N-t-Bu}2Al] (2), and the diethyl ether adduct [Et2O·Li{N(t-Bu)CH2CH2N-t-Bu} 2Al] (3), respectively. The reaction of the diethyl ether adduct 3 with 2 equiv of the chelating nitrogen Lewis bases TMEDA (≡N,N,N',N'-tetramethylethylenediamine) and t-Bu2DAB (≡N,N'-di-tert-butyl-1,4-diazabutadiene) in diethyl ether affords the ionic complex [Li(TMEDA)2][Al{[N(t-Bu)CH2]2}2] (4) and a mixture of the paramagnetic species [Li(t-BuDAB)2] and [Al{[N(t-Bu)CH2]2}2]. which cocrystallize 5, respectively. The reaction of the diethyl ether adduct 3 with 0.5 equiv of HgCl2 yields the neutral paramagnetic species [Al{[N(t-Bu)CH2]2}2] (6). Crystals of 2 are triclinic, of space group P1̄ (No. 2), with a = 15.894(5) Å, b = 15.473(5) Å, c = 9.975(3) Å, α = 93.74(2)°, β= 91.97(2)°, γ = 102.07(3)°, and Z = 4. Crystals of 3 are monoclinic, of space group C2/c (No. 15), with a = 15.835(5) Å, b = 12.054(3) Å, c = 16.456(5) Å, β = 111.56(3)°, and Z = 4. Crystals of 4 are orthorhombic, of space group Pbca (No. 61), with a = 19.349(4) Å, b = 22.227(7) Å, c = 19.070(3) A. and Z = 8. Crystals of 5 are orthorhombic, of space group Pmmn (No. 59). with a = 13.874(4) Å, b = 13.473(6) Å, c = 12.717(3) Å, and Z = 2. Crystals of 6 are monoclinic. of space group C2/c (No. 15), with a = 16.721(4) Å, b = 9.454(4) Å, c = 16.460(8) Å, β= 113.27(3), and Z = 4.

Original languageEnglish
Pages (from-to)2795-2803
Number of pages9
JournalInorganic Chemistry
Volume36
Issue number13
DOIs
Publication statusPublished - 1 Dec 1997
Externally publishedYes

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