Cole, Marcus L., Davies, Aaron J., Jones, Cameron, Junk, Peter C., McKay, Alasdair I., and Stasch, Andreas (2015) Aluminum and indium complexes derived from guanidines, triazenes, and amidines. Zeitschrift für Anorganische und Allgemeine Chemie, 641 (12-13). pp. 2233-2244.

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Abstract

The reaction of guanidines, triazenes, amidines, and lithium amidinates with trimethylamine alane ([AlH3(NMe3)]), lithium tetrahydridoaluminate, trimethylaluminum, aluminum trichloride, and indium trichloride is reported. Equimolar reactions utilising hindered N,N'-bis(2, 6-diisopropylphenyl)guanidines afford [{AlX2L}n] species through hydrogen elimination (X = H) from [AlH3(NMe3)] (n = 2) with HCGiso (1), HDGiso (2), or HDPiso (3) [CGiso = N,N'-bis(2, 6-disopropylphenyl)-N"-dicyclohexylguanidinate, DGiso = N,N',N"-tris(2, 6-diisopropylphenyl)guanidinate, DPiso = N,N'-bis(2, 6-diisopropylphenyl)-P-2, 6-diisopropylphenylphosphguanidinate], or through methane elimination (X = Me) from AlMe3 [n = 1, L = CGiso (5)]. The analogous reactions of the triazene HTiso with LiAlH4 and AlMe3 selectively afford [AlH(Tiso)2] (4) and [AlMe2(Tiso)] (6), respectively [Tiso = 1, 3-bis(2, 6-diisopropylphenyl)triazenide]. Reactions of N,N'-bis(aryl)formamidines/ates with half an equivalent of AlMe3/AlCl3 result in [AlXL2] complexes [X = Me; L = Fxy (7) or Fet (8); X = Cl; L = Fet (9) or L = Fiso (10)] [Fxy = N,N'-bis(2, 6-dimethylphenyl)formamidinate, Fet = N,N'-bis(2, 6-diethylphenyl)formamidinate, Fiso = N,N'-bis(2, 6-diisopropylphenyl)formamidinate]. Treatment of 1 with one equivalent of I2 yields [AlI2(CGiso)] (11). Attempts to prepare [InCl2L] congeners of 11 with L = Fxy and Fet led to the isolation of prodigious quantities of [InCl3(HFxy)2] (12) and [InCl2(Fet)(HFet)] (13) due to adventitious water. The X-ray crystal structures of 1–13 are reported.

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