Treatment of tripodal tris(3-tett-butyl-2-hydroxy-5-methylbenzyl)amine (L) with 1 equiv of trimethylaluminum in toluene gave the stable proalumatrane (AIL) (1) [wherein L = tris(3-tert-butyl-5-methyl-2-oxidobenzyl)amine] featuring a distorted trigonal monopyramidal four-coordinate aluminum geometry. An analogous reaction uses the less sterically congested isomer of L, namely, tris(5-tert-butyl-2-hydroxy-3-methylbenzyl)amine provided dimeric (AIL')2 (2) [wherein L' = tris(5-tert-butyl-3-methyl-2-oxidobenzyl)amine], which contains two bridging alumatrane moieties possessing five-coordinate TBP aluminum geometries. Reaction of AIL with water provided the adduct H2O center dot AIL (3), a species that is representative of a coordinatively stabilized intermediate in the hydrolysis of an aluminum alkoxide. Theoretical calculations revealed that considerable stabilization energy is obtained by the coordination of a water molecule to the tetracoordinate aluminum in AIL and that this result is consistent with the postulate that the Lewis acidity of AIL exceeds that of boron trifluoride, despite the presence of the transannular N -> Al bond in AIL.