Mukhopadhyay, Tufan K. Flores, Marco Groy, Thomas L. Trovitch, Ryan J. A Highly Active Manganese Precatalyst for the Hydrosilylation of Ketones and Esters The reduction of (<sup>Ph<sub>2</sub>PPr</sup>PDI)­MnCl<sub>2</sub> allowed the preparation of the formally zerovalent complex, (<sup>Ph<sub>2</sub>PPr</sup>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<sup>–1</sup> in the absence of solvent. Loadings as low as 0.01 mol % were employed, and (<sup>Ph<sub>2</sub>PPr</sup>PDI)Mn was found to mediate the atom-efficient utilization of Si–H bonds to form quaternary silane products. (<sup>Ph<sub>2</sub>PPr</sup>PDI)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C–O bond. Electronic structure investigation of (<sup>Ph<sub>2</sub>PPr</sup>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. Active Manganese Precatalyst;Electronic structure investigation;PPr;Ph;form quaternary silane products;TOF;carbonyl substituent;metal center;PDI;electron transfer;atom-efficient utilization;bond 2014-01-22
    https://acs.figshare.com/articles/journal_contribution/A_Highly_Active_Manganese_Precatalyst_for_the_Hydrosilylation_of_Ketones_and_Esters/2330101
10.1021/ja4116346.s004