A Pentacoordinate Mn(II) Precatalyst That Exhibits Notable Aldehyde and Ketone Hydrosilylation Turnover Frequencies

被引：55

作者：

Ghosh, Chandrani ^{[1
]}

Mukhopadhyay, Tufan K. ^{[1
]}

Flores, Marco ^{[1
]}

Groy, Thomas L. ^{[1
]}

Trovitch, Ryan J. ^{[1
]}

机构：

[1] Arizona State Univ, Sch Mol Sci, Tempe, AZ 85287 USA

来源：

INORGANIC CHEMISTRY | 2015年 / 54卷 / 21期

关键词：

CATALYZED ASYMMETRIC HYDROSILYLATION; HETEROCYCLIC CARBENE COMPLEXES; ENANTIOSELECTIVE HYDROSILYLATION; CARBONYL-COMPOUNDS; IRON COMPLEXES; SELECTIVE REDUCTION; EFFICIENT CATALYSTS; ALKYL COMPLEXES; CHIRAL LIGANDS; PINCER LIGANDS;

D O I：

10.1021/acs.inorgchem.5b01825

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

Heating (THF)(2)MnCl2 in the presence of the pyridine-substituted bis(imino)pyridine ligand, (PDI)-P-PyEt, allowed preparation of the respective dihalide complex, ((PDI)-P-PyEt)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, (kappa(5)-N,N,N,N,N-(PyEt)PDEA)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, (kappa(5)-N,N,N,N,N-(PyEt)PDEA)Mn was determined to be an effective precatalyst for the hydrosilylation of aldehydes and ketones, exhibiting turnover frequencies of up to 2475 min1 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)(Bu-n)]. The aldehyde hydrosilylation activity observed for (kappa(5)-N,N,N,N,N-(PyEt)PDEA)Mn renders it one of the most efficient first-row transition metal catalysts for this transformation reported to date.

引用

页码：10398 / 10406

页数：9

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