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Updated: May 4, 2026

Imine Metathesis by Silica-Supported Catalysts Using the Methodology of Surface Organometallic Chemistry
Published on: October 18, 2019
A highly active manganese precatalyst for the hydrosilylation of ketones and esters
Tufan K Mukhopadhyay1, Marco Flores, Thomas L Groy
1Department of Chemistry and Biochemistry, Arizona State University , Tempe, Arizona 85287, United States.
Abstract:
The reduction of ((Ph2PPr)PDI)MnCl2 allowed the preparation of the formally zerovalent complex, ((Ph2PPr)PDI)Mn, which features a pentadentate bis(imino)pyridine chelate. This complex is a highly active precatalyst for the hydrosilylation of ketones, exhibiting TOFs of up to 76,800 h(-1) in the absence of solvent. Loadings as low as 0.01 mol % were employed, and ((Ph2PPr)PDI)Mn was found to mediate the atom-efficient utilization of Si-H bonds to form quaternary silane products. ((Ph2PPr)PDI)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. Electronic structure investigation of ((Ph2PPr)PDI)Mn revealed that this complex possesses an unpaired electron on the metal center, rendering it likely that catalysis takes place following electron transfer to the incoming carbonyl substituent.
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