摘要
The reactivities of [C 4 H 2 N(CH 2 NMe 2 ) 2 ]AlH 2 (1) with primary and secondary amines, phenols, ketones, and phenyl isothiocyanate were examined. Reactions of 1 with one or two equivalents of 2,6-dichloroaniline in methylene chloride generated [C 4 H 2 N(CH 2 NMe 2 ) 2 ] AlH(NHC 6 H 3 -2,6-Cl 2 ) (2) and [C 4 H 2 N(CH 2 NMe 2 ) 2 ] Al(NHC 6 H 3 -2,6-Cl 2 ) 2 (3), respectively, following hydrogen elimination. Similarly, the reactions of 1 with one or two equivalents of carbazole afforded [C 4 H 2 N(CH 2 NMe 2 ) 2 ]AlH(NC 12 H 8 ) (4) or [C 4 H 2 N(CH 2 NMe 2 ) 2 ]Al(NC 12 H 8 ) 2 (5) by deprotonating the acidic N-H of carbazole. Reacting 1 with one equivalent of 2,6-diisopropylphenol in diethyl ether formed an aluminium phenoxo compound [C 4 H 2 N(CH 2 NMe 2 ) 2 ]AlH(OC 6 H 3 -2,6- i Pr 2 ) (6), by deprotonation of phenol as well with the elimination of one equivalent hydrogen. Further reaction of 6 with one equivalent of 2,4,6-trimethylacetophenone in methylene chloride generated [C 4 H 2 N(CH 2 NMe 2 ) 2 ] Al(OC 6 H 3 -2,6- i Pr 2 )[OC(CH 2 )(C 6 H 2 -2,4,6-Me 3 )] (7) by deprotonating the methyl proton of the acetophenone. Similar deprotonation occurred when 1 reacted with two equivalents of 2,4,6-trimethylacetophenone in methylene chloride to generate [C 4 H 2 N(CH 2 NMe 2 ) 2 ]Al[OC(CH 2 )(C 6 H 2 -2,4,6-Me 3 )] 2 (8). Compounds [C 4 H 2 N(CH 2 NMe 2 ) 2 ] Al(OCHPh 2 ) 2 (9), and [C 4 H 2 N(CH 2 NMe 2 ) 2 ]Al(SCHNPh) 2 (10) could also be obtained by reacting 1 with two equivalents of benzophenone and phenyl isothiocyanate, respectively through hydroalumination. The 1 H NMR spectra of 10 showed broad signals for the CH 2 N and NMe 2 groups, which represent dynamical fluctuations of the molecules in solution state. The estimated energy barrier (ΔG c ‡ ) from the coalescence temperature for the fluctuation was estimated at 17.1 Kcal mol -1 . The solid-state structures of compounds 2, 3, 5, 7, 9, and 10 have been determined. © 2009 The Royal Society of Chemistry.