Synthesis, Characterization, and Stability of Dealkylated Salen-Supported Aluminum Phosphates

Three salen aluminum bromide compounds salen(tBu)AlBr (1) (salen = N,N′-ethylenebis(3,5-di-tert-butylsalicylideneimine)), salpen(tBu)AlBr (2) (salpen = N,N′-propylenebis(3,5-di-tert-butylsalicylideneimine)), and salophen(tBu)AlBr (3) (salophen = N,N′-o-phenylenenebis(3,5-di-tert-butylsalicylideneimine) were evaluated for their potential use as dealkylation agents with a series of organophosphates. These reactions led to the aluminum phosphate compounds containing six-coordinate aluminum centers and hydrolytically stable P-O-C bonds: 4 = [salen(tBu)AlOP(O)(OMe)2]n, 5 = [salen(tBu)AlOP(O)(OEt)2]n, 6 = [salen(tBu)AlOP(O)(OPh)2]n, 7 = [salophen(tBu)AlOP(O)(OMe)2]n, 8 = [salpen(tBu)AlOP(O)(OiPr)2]2, 9 = (salen(tBu)AlO)3PO, 10 = (salpen(tBu)AlO)3PO, 11 = (salophen(tBu)AlO)3PO. All the compounds were characterized by 1H, 13C, 27Al, and 31P NMR, IR, and mass spectrometry. Furthermore, compounds 4-8 were structurally characterized by single-crystal X-ray diffraction. The potential hydrolysis of these compounds was modeled with 4 and demonstrated the unique stability of the final product and ease of isolation.