Stepwise MetalLigand Cooperation by a Reversible Aromatization/Deconjugation Sequence in Ruthenium Complexes with a Tetradentate Phenanthroline-Based Ligand

被引：46

作者：

Langer, Robert ^{[1
]}

Fuchs, Ido ^{[1
]}

Vogt, Matthias ^{[1
]}

Balaraman, Ekambaram ^{[1
]}

Diskin-Posner, Yael ^{[2
]}

Shimon, Linda J. W. ^{[2
]}

Ben-David, Yehoshoa ^{[1
]}

Milstein, David ^{[1
]}

机构：

[1] Weizmann Inst Sci, Dept Organ Chem, IL-76100 Rehovot, Israel

[2] Weizmann Inst Sci, Dept Chem Res Support, IL-76100 Rehovot, Israel

来源：

CHEMISTRY-A EUROPEAN JOURNAL | 2013年 / 19卷 / 10期

基金：

欧洲研究理事会;

关键词：

cooperative effects; coordination chemistry; dehydrogenation; homogeneous catalysis; ruthenium; HOMOGENEOUS CATALYTIC-HYDROGENATION; ASYMMETRIC HYDROGENATION; PINCER COMPLEXES; BOND ACTIVATION; EFFICIENT HYDROGENATION; KETONE HYDROGENATION; HYDRIDE ELIMINATION; RHODIUM(I) AMIDES; ALCOHOLS; AMINES;

D O I：

10.1002/chem.201204003

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

The synthesis and reactivity of ruthenium complexes containing the tetradentate phenanthroline-based phosphine ligand 2,9-bis((di-tert-butylphosphino)methyl)-1,10-phenanthroline (PPhenP) is described. The hydrido chloro complex [RuHCl(PPhenP)] (2) undergoes facile dearomatization upon deprotonation of the benzylic position, to give [RuH(PPhenP-H)] (4). Addition of dihydrogen to 4 causes rearomatization of the phenanthroline moiety to trans-[Ru(H)2(PPhenP)] (5), followed by hydrogenation of an aromatic heterocycle in the ligand backbone, to give a new dearomatized and deconjugated complex [RuH(PPhenP*-H)] (6). These aromatization/deconjugation steps of the coordinated ligand were demonstrated to be reversible and operative in the dehydrogenation of primary alcohols without the need for a hydrogen acceptor. This aromatization/deconjugation sequence constitutes an unprecedented mode of a stepwise cooperation between the metal center and the coordinated ligand.

引用

页码：3407 / 3414

页数：8

共 60 条

[1] A succession of isomers of ruthenium dihydride complexes. Which one is the ketone hydrogenation catalyst? [J].

Abbel, R ;

Abdur-Rashid, K ;

Faatz, M ;

Hadzovic, A ;

Lough, AJ ;

Morris, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2005, 127 (06) :1870-1882

[2] 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

[3] Catalytic cycle for the asymmetric hydrogenation of prochiral ketones to chiral alcohols:: Direct hydride and proton transfer from chiral catalysts trans-Ru(H)2(diphosphine)(diamine) to ketones and direct addition of dihydrogen to the resulting hydridoamido complexes [J].

Abdur-Rashid, K ;

Faatz, M ;

Lough, AJ ;

Morris, RH .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (30) :7473-7474

[4]

[Anonymous], 2006, ANGEW CHEM, DOI DOI 10.1002/ANGE.200503771

[5]

[Anonymous], 2011, Angew. Chem, DOI DOI 10.1002/ANGE.201105876

[6]

Balaraman E., 2011, ANGEW CHEM INT EDIT, V123, P11906, DOI DOI 10.1002/ANGE.201106612

[7] 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

[8]

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

[9] 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

[10]

Beller M., 2004, TRANSITION METALS OR

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