Stable Mg Dication Weakly Stabilized/Coordinated in Solution: Synthesis, Structure, Reactivity, and Use in Catalysis.

The first soluble and stable Mg dication stabilized only by weakly coordinating and chemically robust carborate anions [HexCBCl] is described. Mg[HexCBCl] (1), prepared by reaction of Mg(Bu) with 2 equiv of [PhC][HexCBCl], consists, in the solid state, of a central Mg surrounded by two [HexCBCl] anions. In solution, experimental and classical molecular dynamics simulations (cMD) agree with cation/anion association being retained, reflecting the high electrophilicity of the Mg center. Yet, reflecting only weak anion/cation interactions, species 1 polymerizes 1-hexene and coordinates alkynes. However, 1 displays no reaction with HSiEt at room temperature, consistent with a low hydridicity of the hard (HSAB) Mg center. Contrasting with 1 (FIA = 264 kJ mol; FIA: Fluoride Ion Affinity), salt Mg[(nBu)NBHCl] (2), incorporating the more basic ammoniododecaborate [(nBu)NBHCl] anion, is significantly less Lewis acidic (FIA = 214.7 kJ mol) and unreactive with alkenes and alkynes. Salt 1 effectively catalyzes alkene/alkyne hydrosilylation via an initial alkene/alkyne coordination/initiation, as suggested by experimental and computational data. It also efficiently catalyzes (with a catalyst loading down to 0.1 mol%) the hydrosilylation of CO to CH in the presence of HSiEt. Salt 1 smoothly promotes the catalytic transfer hydrogenation of 1,1-diphenylethylene, and it is also an active imine hydrogenation catalyst in the presence of H.