Metal-Ligand Cooperation Facilitates Bond Activation and Catalytic Hydrogenation with Zinc Pincer Complexes

被引:62
作者
Rauch, Michael [1 ]
Kar, Sayan [1 ]
Kumar, Amit [1 ]
Avram, Liat [2 ]
Shimon, Linda J. W. [2 ]
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
基金
欧洲研究理事会;
关键词
ENANTIOSELECTIVE HYDROSILYLATION; COORDINATION CHEMISTRY; PNP; REACTIVITY; IMINES; DEHYDROGENATION; REDUCTION; ALUMINUM; BEARING; H-2;
D O I
10.1021/jacs.0c05500
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
A series of PNP zinc pincer complexes capable of bond activation via aromatization/dearomatization metal-ligand cooperation (MLC) were prepared and characterized. Reversible heterolytic N-H and H-H bond activation by MLC is shown, in which hemilability of the phosphorus linkers plays a key role. Utilizing this zinc pincer system, basefree catalytic hydrogenation of imines and ketones is demonstrated. A detailed mechanistic study supported by computation implicates the key role of MLC in facilitating effective catalysis. This approach offers a new strategy for (de)hydrogenation and other catalytic transformations mediated by zinc and other main group metals.
引用
收藏
页码:14513 / 14521
页数:9
相关论文
共 68 条
[1]   Cooperative Bond Activation and Catalytic Reduction of Carbon Dioxide at a Group 13 Metal Center [J].
Abdalla, Joseph A. B. ;
Riddlestone, Ian M. ;
Tirfoin, Remi ;
Aldridge, Simon .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2015, 54 (17) :5098-5102
[2]   POP-type ligands: Variable coordination and hemilabile behaviour [J].
Adams, Gemma M. ;
Weller, Andrew S. .
COORDINATION CHEMISTRY REVIEWS, 2018, 355 :150-172
[3]   First-Row Transition Metal (De)Hydrogenation Catalysis Based On Functional Pincer Ligands [J].
Alig, Lukas ;
Fritz, Maximilian ;
Schneider, Sven .
CHEMICAL REVIEWS, 2019, 119 (04) :2681-2751
[4]  
[Anonymous], 2006, The Handbook of Homogeneous Hydrogenation
[5]   Imine hydrogenation with simple alkaline earth metal catalysts [J].
Bauer, Heiko ;
Alonso, Mercedes ;
Farber, Christian ;
Elsen, Holger ;
Pahl, Jurgen ;
Causero, Andrea ;
Ballmann, Gerd ;
De Proft, Frank ;
Harder, Sjoerd .
NATURE CATALYSIS, 2018, 1 (01) :40-47
[6]   Catalysis by Aluminum(III) Complexes of Non-Innocent Ligands [J].
Berben, Louise A. .
CHEMISTRY-A EUROPEAN JOURNAL, 2015, 21 (07) :2734-2742
[7]   Hydrogenation without a transition-metal catalyst:: On the mechanism of the base-catalyzed hydrogenation of ketones [J].
Berkessel, A ;
Schubert, TJS ;
Müller, TN .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2002, 124 (29) :8693-8698
[8]  
Braunstein P, 2001, ANGEW CHEM INT EDIT, V40, P680, DOI 10.1002/1521-3773(20010216)40:4<680::AID-ANIE6800>3.0.CO
[9]  
2-0
[10]   What a Difference a 5f Element Makes: Trivalent and Tetravalent Uranium Halide Complexes Supported by One and Two Bis[2-(diisopropylphosphino)-4-methylphenyl]amido (PNP) Ligands [J].
Cantat, Thibault ;
Scott, Brian L. ;
Morris, David E. ;
Kiplinger, Jaclueline L. .
INORGANIC CHEMISTRY, 2009, 48 (05) :2114-2127