Isolable Silicon-Based Polycations with Lewis Superacidity.

Molecular silicon polycations of the types R2 Si2+ and RSi3+ (R=H, organic groups) are elusive Lewis superacids and currently unknown in the condensed phase. Here, we report the synthesis of a series of isolable terpyridine-stabilized R2 Si2+ and RSi3+ complexes, [R2 Si(terpy)]2+ (R=Ph 12+ ; R2 =C12 H8 22+ , (CH2 )3 32+ ) and [RSi(terpy)]3+ (R=Ph 43+ , cyclohexyl 53+ , m-xylyl 63+ ), in form of their triflate salts. The stabilization of the latter is achieved through higher coordination and to the expense of reduced fluoride-ion affinities, but a significant level of Lewis superacidity is nonetheless retained as verified by theory and experiment. The complexes activate C(sp3 )-F bonds, as showcased by stoichiometric fluoride abstraction from 1-fluoroadamantane (AdF) and the catalytic hydrodefluorination of AdF. The formation of the crystalline adducts [2(F)]+ and [5(H)]2+ documents in particular the high reactivity towards fluoride and hydride donors.