TY - DATA T1 - A Highly Active Manganese Precatalyst for the Hydrosilylation of Ketones and Esters PY - 2014/01/22 AU - Tufan K. Mukhopadhyay AU - Marco Flores AU - Thomas L. Groy AU - Ryan J. Trovitch UR - https://acs.figshare.com/articles/dataset/A_Highly_Active_Manganese_Precatalyst_for_the_Hydrosilylation_of_Ketones_and_Esters/2330092 DO - 10.1021/ja4116346.s001 L4 - https://ndownloader.figshare.com/files/3967720 KW - Active Manganese Precatalyst KW - Electronic structure investigation KW - PPr KW - Ph KW - form quaternary silane products KW - TOF KW - carbonyl substituent KW - metal center KW - PDI KW - electron transfer KW - atom-efficient utilization KW - bond N2 - The reduction of (Ph2PPrPDI)­MnCl2 allowed the preparation of the formally zerovalent complex, (Ph2PPrPDI)­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 (Ph2PPrPDI)Mn was found to mediate the atom-efficient utilization of Si–H bonds to form quaternary silane products. (Ph2PPrPDI)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C–O bond. Electronic structure investigation of (Ph2PPrPDI)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. ER -