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

Raya-Barón, Á.; Ortuño, M. A.; Oña-Burgos, P.; Rodríguez-Diéguez, A.; Langer, R.; Cramer, C. J.; Kuzu, I.; Fernández, I.
Organometallics 2016, 35, 4083 (doi:10.1021/acs.organomet.6b00765)

A new iron complex based on a non-innocent 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.