Steric Stabilization of a Monomeric Proalumatrane: Experimental and Theoretical Studies

Treatment of tripodal tris(3-tert-butyl-2-hydroxy-5-methylbenzyl)amine (L) with 1 equiv of trimethylaluminum in toluene
gave the stable proalumatrane (AlL) (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 (AlL‘)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 AlL with water provided the adduct H2O·AlL (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 AlL and that this result is consistent with the postulate that the Lewis acidity of AlL
exceeds that of boron trifluoride, despite the presence of the transannular N→Al bond in AlL.