Abstract
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 language | English |
|---|---|
| Pages (from-to) | 882-885 |
| Number of pages | 4 |
| Journal | Journal of the American Chemical Society |
| Volume | 136 |
| Issue number | 3 |
| DOIs | |
| Publication status | Published - Jan 22 2014 |
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ASJC Scopus subject areas
- Chemistry(all)
- Catalysis
- Biochemistry
- Colloid and Surface Chemistry
Cite this
A highly active manganese precatalyst for the hydrosilylation of ketones and esters. / Mukhopadhyay, Tufan K.; Flores, Marco; Groy, Thomas L.; Trovitch, Ryan.
In: Journal of the American Chemical Society, Vol. 136, No. 3, 22.01.2014, p. 882-885.Research output: Contribution to journal › Article
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TY - JOUR
T1 - A highly active manganese precatalyst for the hydrosilylation of ketones and esters
AU - Mukhopadhyay, Tufan K.
AU - Flores, Marco
AU - Groy, Thomas L.
AU - Trovitch, Ryan
PY - 2014/1/22
Y1 - 2014/1/22
N2 - 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.
AB - 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.
UR - http://www.scopus.com/inward/record.url?scp=84892962024&partnerID=8YFLogxK
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U2 - 10.1021/ja4116346
DO - 10.1021/ja4116346
M3 - Article
AN - SCOPUS:84892962024
VL - 136
SP - 882
EP - 885
JO - Journal of the American Chemical Society
JF - Journal of the American Chemical Society
SN - 0002-7863
IS - 3
ER -