Aluminum and Indium Complexes derived from Guanidines, Triazenes, and Amidines

作者：Cole Marcus L; Davies Aaron J; Jones Cameron; Junk Peter C^*; Mckay Alasdair I; Stasch Andreas

来源：Zeitschrift fur Anorganische und Allgemeine Chemie, 2015, 641(12-13): 2233-2244.

DOI：10.1002/zaac.201500556

• Alkyl
• Aluminum
• Amidines
• Amidinates
• Formamidines
• Formamidinates
• Guanidinates
• Halides
• Hydrides
• Indium
• Methyl
• Phosphaguanidinates
• Triazenes
• Triazenides

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( 2,6disopropylphenyl)- 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.

• 出版日期2015-10