Highly Electrophilic Mononuclear Cationic Aluminum Alkoxide Complexes: Syntheses, Reactivity and Catalytic Applications.

Abstract

Herein, we report on the synthesis of β-diketiminate supported aluminum complexes bearing terminal alkoxide and mono-thiol functional groups: LAlOMe(Et) (2), LAlOtBu(Et) (3), and LAlSH(Et) (4), (L= [HC{C(Me)N-(2,6-iPr2C6H3)}2]). Complexes 2 and 3 are further utilized as synthons to generate some fascinating cationic aluminum alkoxide complexes, [LAlOMe(µ-OMe)-Al(Et)L][EtB(C6F5)3] (5), [LAlOMe(OEt2)][EtB(C6F5)3] (6), and [LAlOtBu(OEt2)][EtB(C6F5)3] (8). These electrophilic cationic species are well characterized by spectroscopic and crystallographic techniques. The assessment of Lewis acidity by the Gutmann-Beckett method revealed superior Lewis acidity of the cations substituted with electron demanding alkoxy groups in comparison to the known methyl analogue [LAlMe][B(C6F5)4]. This has been further endorsed by computational calculations to determine the NBO charges and hydride ion affinity for complexes 6 and 8. These complexes are also capable of activating triethylsilane in stoichiometric reactions. The applicability of these complexes has been realized in the hydrosilylation of ethers, carbonyls, and olefines. Additionally, the solid state structure of a new THF stabilized aluminum halide cation [LAlCl(THF)][B(C6F5)4] (11) has also been reported.