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

Herein, we report the synthesis of ß-diketiminate-supported aluminium 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-iPr2 C6 H3 )}2 ]). Complexes 2 and 3 are further used as synthons to generate the fascinating cationic aluminium alkoxide complexes, [LAlOMe(µ-OMe)-Al(Et)L][EtB(C6 F5 )3 ] (5), [LAlOMe(OEt2 )][EtB(C6 F5 )3 ] (6), and [LAlOtBu(OEt2 )][EtB(C6 F5 )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(C6 F5 )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 aluminium halide cation [LAlCl(THF)][B(C6 F5 )4 ] (11) has also been reported.