A Persistent Alkylaluminum Peroxide: Surprising Stability of a Molecule with Strong Reducing and Oxidizing Functions in Close Proximity

Abstract

The reaction of the beta-diketiminato coordinated aluminum dihydride, [{HC[C(Me)N-C(6)H(5)](2)}AlH(2)] (1) with bis(trimethylsilyl)methyllithium afforded the monoalkylaluminum derivative [{HC[C(Me)N-C(6)H(5)](2)}Al(H)-CH(SiMe(3))(2)] (2) by the precipitation of lithium hydride. Interestingly, treatment of 2 with tert-butyl hydrogenperoxide did not result in the formation of the simple oxidation product containing a hydroxo or alkoxo group, instead, elemental hydrogen was released and the hydrido ligand attached to aluminum was replaced by an intact tert- butylperoxo group. The Al-C bond, which normally is extremely sensitive towards an attack of oxygen, was not affected. Hence, the product exhibits quite conflicting chemical properties in a close proximity: a strongly reducing Al-C bond beside an oxidizing peroxo group.