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

Tufan K. Mukhopadhyay; Marco Flores; Thomas L. Groy; Ryan Trovitch

doi:10.1021/ja4116346

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

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

Molecular Sciences, School of (SMS)

Research output: Contribution to journal › Article › peer-review

136 Scopus citations

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. (Ph₂^PPrPDI)Mn was also shown to catalyze the dihydrosilylation of esters following cleavage of the substrate acyl C-O bond. Electronic structure investigation of (Ph ₂^PPrPDI)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 (US)
Pages (from-to)	882-885
Number of pages	4
Journal	Journal of the American Chemical Society
Volume	136
Issue number	3
DOIs	https://doi.org/10.1021/ja4116346
State	Published - Jan 22 2014

ASJC Scopus subject areas

Catalysis
General Chemistry
Biochemistry
Colloid and Surface Chemistry

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10.1021/ja4116346

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title = "A highly active manganese precatalyst for the hydrosilylation of ketones and esters",

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.",

author = "Mukhopadhyay, {Tufan K.} and Marco Flores and Groy, {Thomas L.} and Ryan Trovitch",

year = "2014",

month = jan,

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doi = "10.1021/ja4116346",

language = "English (US)",

volume = "136",

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journal = "Journal of the American Chemical Society",

issn = "0002-7863",

publisher = "American Chemical Society",

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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.

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DO - 10.1021/ja4116346

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JO - Journal of the American Chemical Society

JF - Journal of the American Chemical Society

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

Abstract

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CCDC 958769: Experimental Crystal Structure Determination

CCDC 958770: Experimental Crystal Structure Determination

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

Abstract

ASJC Scopus subject areas

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Datasets

CCDC 958769: Experimental Crystal Structure Determination

CCDC 958770: Experimental Crystal Structure Determination

Cite this