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

Tufan K. Mukhopadhyay, Marco Flores, Thomas L. Groy, Ryan J. Trovitch

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The reduction of (Ph2 PPrPDI)MnCl2 allowed the preparation of the formally zerovalent complex, (Ph2 PPrPDI)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 (Ph2 PPrPDI)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 (Ph 2PPrPDI)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.

Original languageEnglish
Pages (from-to)882-885
Number of pages4
JournalJournal of the American Chemical Society
Issue number3
Publication statusPublished - Jan 22 2014


ASJC Scopus subject areas

  • Catalysis
  • Chemistry(all)
  • Biochemistry
  • Colloid and Surface Chemistry

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