Aldehyde Binding through Reversible C-C Coupling with the Pincer Ligand upon Alcohol Dehydrogenation by a PNP-Ruthenium Catalyst

被引：122

作者：

Montag, Michael ^{[1
]}

Zhang, Jing ^{[1
]}

Milstein, David ^{[1
]}

机构：

[1] Weizmann Inst Sci, Dept Organ Chem, IL-76000 Rehovot, Israel

来源：

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY | 2012年 / 134卷 / 25期

基金：

欧洲研究理事会;

关键词：

CARBON BOND FORMATION; INDUCED O-2 EVOLUTION; AROMATIZATION-DEAROMATIZATION; HYDRIDE ELIMINATION; ELECTRON-RICH; H-H; COMPLEX; HYDROGENATION; COOPERATION; ACTIVATION;

D O I：

10.1021/ja303121v

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Primary alcohol dehydrogenation by a PNP-Ru(II) catalyst was probed by low-temperature NMR experiments. Facile dehydrogenation occurred at -30 degrees C, but the resulting aldehydes were not found in solution, as they were trapped by the catalyst through a new mode of metal-ligand cooperation involving Ru-O coordination and an unusual, highly reversible C-C coupling with the PNP pincer ligand.

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页码：10325 / 10328

页数：4

相关论文

共 48 条

[1] Mechanism of the hydrogenation of ketones catalyzed by trans-dihydrido(diamine)ruthenium(II) complexes [J].

Abdur-Rashid, K ;

Clapham, SE ;

Hadzovic, A ;

Harvey, JN ;

Lough, AJ ;

Morris, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (50) :15104-15118

[2] Unprecedented Catalytic Hydrogenation of Urea Derivatives to Amines and Methanol [J].

Balaraman, Ekambaram ;

Ben-David, Yehoshoa ;

Milstein, David .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (49) :11702-11705

[3]

Balaraman E, 2011, NAT CHEM, V3, P609, DOI [10.1038/NCHEM.1089, 10.1038/nchem.1089]

[4] Direct Hydrogenation of Amides to Alcohols and Amines under Mild Conditions [J].

Balaraman, Ekambaram ;

Gnanaprakasam, Boopathy ;

Shimon, Linda J. W. ;

Milstein, David .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (47) :16756-16758

[5] Metal-ligand cooperation in C-H and H2 activation by an electron-rich PNPIr(I) system:: Facile ligand dearomatization-aromatization as key steps [J].

Ben-Ari, Eyal ;

Leitus, Gregory ;

Shimon, Linda J. W. ;

Milstein, David .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2006, 128 (48) :15390-15391

[6] Osmium and Ruthenium Catalysts for Dehydrogenation of Alcohols [J].

Bertoli, Marcello ;

Choualeb, Aldjia ;

Lough, Alan J. ;

Moore, Brandon ;

Spasyuk, Denis ;

Gusev, Dmitry G. .

ORGANOMETALLICS, 2011, 30 (13) :3479-3482

[7] Hydride elimination from an iridium(III) alkoxide complex:: a case in which a vacant cis coordination site is not required [J].

Blum, O ;

Milstein, D .

JOURNAL OF ORGANOMETALLIC CHEMISTRY, 2000, 593 :479-484

[8] Mechanistic Insights on the Ruthenium-Catalyzed Hydrogenation of Amides - C-N vs. C-O Cleavage [J].

Cantillo, David .

EUROPEAN JOURNAL OF INORGANIC CHEMISTRY, 2011, (19) :3008-3013

[9] Mechanism for the Light-Induced O2 Evolution from H2O Promoted by Ru(II) PNN Complex: A DFT Study [J].

Chen, Yue ;

Fang, Wei-Hai .

JOURNAL OF PHYSICAL CHEMISTRY A, 2010, 114 (37) :10334-10338

[10] Retardation of β-hydrogen elimination in PNP Pincer complexes of Pd [J].

Fafard, Claudia M. ;

Ozerov, Oleg V. .

INORGANICA CHIMICA ACTA, 2007, 360 (01) :286-292

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