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 27 条

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