Efficient Hydrosilylation of Acetophenone with a New Anthraquinonic Amide-Based Iron Precatalyst

A new iron complex based on a noninnocent anthraquinonic ligand has been synthesized and fully characterized through multiple techniques, including NMR, X-ray crystallography, mass spectrometry, and cyclic voltammetry. Exposure of ketone to that complex in the presence of (EtO)2MeSiH affords the corresponding silylated alcohol. Loadings as low as 0.25 mol % afford excellent yields at room temperature. Quantum–chemical analysis of the catalytic mechanism supports activation of the precatalyst to form a Fe–hydride intermediate, followed by ketone reduction and σ-bond metathesis.