Efficient and selective alkene hydrosilation promoted by weak, double Si–H activation at an iron center

Cationic iron complexes [Cp*((i)Pr(2)MeP)FeH(2)SiHR](+), generated and characterized in solution, are very efficient catalysts for the hydrosilation of terminal alkenes and internal alkynes by primary silanes at low catalyst loading (0.1 mol%) and ambient temperature. These reactions yield only the corresponding secondary silane product, even with SiH(4) as the substrate. Mechanistic experiments and DFT calculations indicate that the high rate of hydrosilation is associated with an inherently low barrier for dissociative silane exchange (product release).