Abstract
Chemo- and regioselectivity are often difficult to control during olefin hydrosilylation catalyzed by d- and f-block metal complexes. The cationic hydride of calcium [CaH](+) stabilized by an NNNN macrocycle was found to catalyze the regioselective hydrosilylation of aliphatic olefins to give anti-Markovnikov products, while aryl-substituted olefins were hydrosilyated with Markovnikov regioselectivity. Ethylene was efficiently hydrosilylated by primary and secondary hydrosilanes to give di- and monoethylated silanes. Aliphatic hydrosilanes were preferred over other commonly employed hydrosilanes: Arylsilanes such as PhSiH(3) underwent scrambling reactions promoted by the nucleophilic hydride, while alkoxy- and siloxy-substituted hydrosilanes gave isolable alkoxy and siloxy calcium derivatives.