Reactivity and derivatization of five-coordinate, chelated aluminum.

The convenient five-coordinate starting materials, Salen((t)Bu)AlCl (Salen((t)Bu) = N,N'-alkylene (or arylene) bis (3,5-di-tert-butyl-2-hydroxybenzylideneamine) (1-4) can be used in a wide range of reactions to form five-coordinate aluminum compounds. Herein, these reagents were used to produce new five-coordinate azides, LAlN(3) (L = Salen((t)Bu) (5), Salpen((t)Bu) (6), and Salomphen((t)Bu) (7)) through trimethylsilylhalide elimination. The decomposition of the azides produce first hydroxide (LAlOH (L = Salen((t)Bu) (8)) and, subsequently in the presence of chlorotrimethylsilane, the siloxide compounds, LAlOSiMe(3) (L = Salen((t)Bu) (9), Salpen((t)Bu) (10), and Salomphen((t)Bu) (11)). Alkane elimination reactions may also be used to access this type of compound as evidenced by the formation of Salomphen((t)Bu)AlOSiPh(3) (12). Additionally, the first structurally characterized five-coordinate monomeric amide, Salcen((t)Bu)AlN(SiMe(3))(2) (13), can prepared by a salt elimination utilizing Salcen((t)Bu)AlCl (4). The compounds were characterized by spectroscopic methods ((1)H and (27)Al NMR, MS, and IR) and, in the case of 2 (Salpen((t)Bu)AlCl), 3 (Salomphen((t)Bu)AlCl) 9, 11, 12, and 13, by X-ray analysis. Several of the compounds were explored as potential catalysts for the living polymerization of propylene oxide.