TY - JOUR
T1 - Aluminum and indium complexes derived from guanidines, triazenes, and amidines
AU - Cole, Marcus L
AU - Davies, Aaron J
AU - Jones, Cameron
AU - Junk, Peter Courtney
AU - McKay, Alasdair I
AU - Stasch, Andreas
N1 - The authors would like to acknowledge the Leverhulme Trust and Australian Research Council (DP110104759, DP09884775) for support of this research, and the EPSRC and Australian Commonwealth for partial studentships (A.J.D. and A.I.M.).
PY - 2015/10/8
Y1 - 2015/10/8
N2 - 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.
AB - 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.
KW - Alkyl
KW - Aluminium
KW - Amidines
KW - Amidinates
KW - Formamidines
KW - Formamidinates
KW - Guanidinates
KW - Halides
KW - Hydrides
KW - Indium
KW - Methyl
KW - Phosphaguanidinates
KW - Triazenes
KW - Triazenides
U2 - 10.1002/zaac.201500556
DO - 10.1002/zaac.201500556
M3 - Article
SN - 0044-2313
VL - 641
SP - 2233
EP - 2244
JO - Zeitschrift für Anorganische und Allgemeine Chemie
JF - Zeitschrift für Anorganische und Allgemeine Chemie
IS - 12-13
ER -