The alkane elimination reaction between Salen(Bu-t)H-2 ligands and diethylaluminum bromide was used to prepare three Salen aluminum bromide compounds salen(Bu-t)AlBr (1) (salen = N,N'-ethylenebis(3,5-di-tert-butylsalicylideneimine)), salpen(Bu-t)AlBr (2) (salpen = N,N'-propylenebis(3,5-di-tert-butylsalicylideneimine)), and salophen(Bu-t)AlBr (3) (salophen = N,N'-o-phenylenenebis(3,5-di-tert-butylsalicylideneimine)). The compounds contain five-coordinate aluminum either in a distorted square pyramidal or a trigonal bipyramidal environment. The bromide group in these compounds could be displaced by triphenylphosphine oxide or triphenyl phosphate to produce the six-coordinate cationic aluminum compounds [salen(Bu-t)Al(Ph3PO)(2)]Br (4), [salpen(Bu-t)Al(Ph3PO)(2)]Br (5), [salophen(Bu-t)Al(Ph3PO)(2)]Br (6), and [salophen(Bu-t)Al{ (PhO)(3)PO)}(2)]Br (7). All the compounds were characterized by H-1, C-13, Al-27, and P-31 NMR, IR, mass spectrometry, and melting point. Furthermore, compounds 1-3 and 5-7 were structurally characterized by single-crystal X-ray diffraction. Compounds 1-3 dealkylated a series of organophosphates in stoichiometric reactions by breaking the ester C-O bond. Also, they were catalytic in the dealkylation reaction between trimethyl phosphate and added boron tribromide.