A highly active manganese precatalyst for the hydrosilylation of ketones and esters

Authors: Mukhopadhyay, T.K., Flores, M., Groy, T.L., and Trovitch, R.J.
Title: A highly active manganese precatalyst for the hydrosilylation of ketones and esters
Source: Journal of the American Chemical Society
Year: 2014
Volume: 136 (3)
Pages: 882–885

ABSTRACT:

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 turnover frequencies of up to 76,800 h-1 in the absence of solvent. Loadings as low as 0.01 mol% have been employed and (Ph2PPrPDI)Mn has been found to mediate the atom-efficient utilization of Si-H bonds to form quaternary silane products. Furthermore, (Ph2PPrPDI)Mn has been shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. The 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.


Date of online publication: Tue, 2013-12-24
Center for Bio-Inspired Solar Fuel Production 
Arizona State University, Room ISTB-5 101, Box 871604, Tempe, AZ 85287-1604 
phone: (480) 965-1548 | fax: (480) 965-5927 | Contact Us