Anionic and Neutral Aluminum Bis(N,N'-di-tert-butylethylenediamide) Complexes: [Al{[N(t-Bu)CH(2)](2)}(2)](-) and [Al{[N(t-Bu)CH(2)](2)}(2)](*).
The reaction of the aluminum triamide [{EtaN(t-Bu)CH(2)CH(2)N-t-Bu}Al{N(t-Bu)CH(2)}(2)] (1) with n-BuLi in hexane and diethyl ether gives the monomeric solvent-free lithium aluminum tetraamide [Li{N(t-Bu)CH(2)CH(2)N-t-Bu}(2)Al] (2), and the diethyl ether adduct [Et(2)O.Li{N(t-Bu)CH(2)CH(2)N-t-Bu}(2)Al] (3), respectively. The reaction of the diethyl ether adduct 3 with 2 equiv of the chelating nitrogen Lewis bases TMEDA ( identical withN,N,N',N'-tetramethylethylenediamine) and t-Bu(2)DAB ( identical withN,N'-di-tert-butyl-1,4-diazabutadiene) in diethyl ether affords the ionic complex [Li(TMEDA)(2)][Al{[N(t-Bu)CH(2)](2)}(2)] (4) and a mixture of the paramagnetic species [Li(t-BuDAB)(2)] and [Al{[N(t-Bu)CH(2)](2)}(2)], which cocrystallize 5, respectively. The reaction of the diethyl ether adduct 3 with 0.5 equiv of HgCl(2) yields the neutral paramagnetic species [Al{[N(t-Bu)CH(2)](2)}(2)] (6). Crystals of 2 are triclinic, of space group P&onemacr; (No. 2), with a = 15.894(5) Å, b = 15.473(5) Å, c = 9.975(3) Å, alpha = 93.74(2) degrees, beta = 91.97(2) degrees, gamma = 102.07(3) degrees, and Z = 4. Crystals of 3are monoclinic, of space group C2/c (No. 15), with a = 15.835(5) Å, b = 12.054(3) Å, c = 16.456(5) Å, beta = 111.56(3) degrees, and Z = 4. Crystals of 4are orthorhombic, of space group Pbca (No. 61), with a = 19.349(4) Å, b = 22.227(7) Å, c = 19.070(3) Å, 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, beta = 113.27(3), and Z = 4.
Gardiner
Michael G.
MG
Departments of Chemistry, Monash University, Clayton, Melbourne, Victoria 3168, Australia, and University of Western Australia, Nedlands, Western Australia 6709, Australia.
Raston
Colin L.
CL
Skelton
Brian W.
BW
White
Allan H.
AH