Abstract
Heating (THF)2MnCl2 in the presence of the pyridine-substituted bis(imino)pyridine ligand, PyEtPDI, allowed preparation of the respective dihalide complex, (PyEtPDI)MnCl2. Reduction of this precursor using excess Na/Hg resulted in deprotonation of the chelate methyl groups to yield the bis(enamide)tris(pyridine)-supported product, (κ5-N,N,N,N,N-PyEtPDEA)Mn. This complex was characterized by single-crystal X-ray diffraction and found to possess an intermediate-spin (S = 3/2) Mn(II) center by the Evans method and electron paramagnetic resonance spectroscopy. Furthermore, (κ5-N,N,N,N,N-PyEtPDEA)Mn was determined to be an effective precatalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 2475 min-1 when employed under solvent-free conditions. This optimization allowed for isolation of the respective alcohols and, in two cases, the partially reacted silyl ethers, PhSiH(OR)2 [R = Cy and CH(Me)(nBu)]. The aldehyde hydrosilylation activity observed for (κ5-N,N,N,N,N-PyEtPDEA)Mn renders it one of the most efficient first-row transition metal catalysts for this transformation reported to date.
| Original language | English |
|---|---|
| Pages (from-to) | 10398-10406 |
| Number of pages | 9 |
| Journal | Inorganic Chemistry |
| Volume | 54 |
| Issue number | 21 |
| DOIs | |
| Publication status | Published - Oct 19 2015 |
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ASJC Scopus subject areas
- Inorganic Chemistry
- Physical and Theoretical Chemistry
Cite this
A Pentacoordinate Mn(II) Precatalyst That Exhibits Notable Aldehyde and Ketone Hydrosilylation Turnover Frequencies. / Ghosh, Chandrani; Mukhopadhyay, Tufan K.; Flores, Marco; Groy, Thomas L.; Trovitch, Ryan.
In: Inorganic Chemistry, Vol. 54, No. 21, 19.10.2015, p. 10398-10406.Research output: Contribution to journal › Article
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TY - JOUR
T1 - A Pentacoordinate Mn(II) Precatalyst That Exhibits Notable Aldehyde and Ketone Hydrosilylation Turnover Frequencies
AU - Ghosh, Chandrani
AU - Mukhopadhyay, Tufan K.
AU - Flores, Marco
AU - Groy, Thomas L.
AU - Trovitch, Ryan
PY - 2015/10/19
Y1 - 2015/10/19
N2 - Heating (THF)2MnCl2 in the presence of the pyridine-substituted bis(imino)pyridine ligand, PyEtPDI, allowed preparation of the respective dihalide complex, (PyEtPDI)MnCl2. Reduction of this precursor using excess Na/Hg resulted in deprotonation of the chelate methyl groups to yield the bis(enamide)tris(pyridine)-supported product, (κ5-N,N,N,N,N-PyEtPDEA)Mn. This complex was characterized by single-crystal X-ray diffraction and found to possess an intermediate-spin (S = 3/2) Mn(II) center by the Evans method and electron paramagnetic resonance spectroscopy. Furthermore, (κ5-N,N,N,N,N-PyEtPDEA)Mn was determined to be an effective precatalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 2475 min-1 when employed under solvent-free conditions. This optimization allowed for isolation of the respective alcohols and, in two cases, the partially reacted silyl ethers, PhSiH(OR)2 [R = Cy and CH(Me)(nBu)]. The aldehyde hydrosilylation activity observed for (κ5-N,N,N,N,N-PyEtPDEA)Mn renders it one of the most efficient first-row transition metal catalysts for this transformation reported to date.
AB - Heating (THF)2MnCl2 in the presence of the pyridine-substituted bis(imino)pyridine ligand, PyEtPDI, allowed preparation of the respective dihalide complex, (PyEtPDI)MnCl2. Reduction of this precursor using excess Na/Hg resulted in deprotonation of the chelate methyl groups to yield the bis(enamide)tris(pyridine)-supported product, (κ5-N,N,N,N,N-PyEtPDEA)Mn. This complex was characterized by single-crystal X-ray diffraction and found to possess an intermediate-spin (S = 3/2) Mn(II) center by the Evans method and electron paramagnetic resonance spectroscopy. Furthermore, (κ5-N,N,N,N,N-PyEtPDEA)Mn was determined to be an effective precatalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 2475 min-1 when employed under solvent-free conditions. This optimization allowed for isolation of the respective alcohols and, in two cases, the partially reacted silyl ethers, PhSiH(OR)2 [R = Cy and CH(Me)(nBu)]. The aldehyde hydrosilylation activity observed for (κ5-N,N,N,N,N-PyEtPDEA)Mn renders it one of the most efficient first-row transition metal catalysts for this transformation reported to date.
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U2 - 10.1021/acs.inorgchem.5b01825
DO - 10.1021/acs.inorgchem.5b01825
M3 - Article
VL - 54
SP - 10398
EP - 10406
JO - Inorganic Chemistry
JF - Inorganic Chemistry
SN - 0020-1669
IS - 21
ER -