Heterolytic Cleavage of Dihydrogen by "Frustrated Lewis Pairs" Comprising Bis(2,4,6-tris(trifluoromethyl)phenyl)borane and Amines: Stepwise versus Concerted Mechanism

被引：85

作者：

Lu, Zhenpin ^{[1
]}

Cheng, Zhonghua ^{[1
]}

Chen, Zhenxia ^{[1
]}

Weng, Linhong ^{[1
]}

Li, Zhen Hua ^{[1
]}

Wang, Huadong ^{[1
]}

机构：

[1] Fudan Univ, Dept Chem, Shanghai Key Lab Mol Catalysis & Innovat Mat, Shanghai 200433, Peoples R China

来源：

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION | 2011年 / 50卷 / 51期

关键词：

amines; boranes; frustrated Lewis pairs; hydrogen; FREE CATALYTIC-HYDROGENATION; MOLECULAR-STRUCTURE; H-2; ACTIVATION; BORANE; REACTIVITY; IMINES; B(C6F5)(3); CARBENE; CRYSTAL; COMPLEX;

D O I：

10.1002/anie.201104999

中图分类号：

O6 [化学];

学科分类号：

0703 ;

摘要：

Channeling the frustration: Frustrated Lewis pairs (FLPs) consisting of Ar F 2BH 1 with NEt 3 or DABCO can activate H 2 under mild conditions. Theoretical calculations suggest two distinct reaction pathways for these two FLPs. For the "more frustrated" Ar F 2BH/NEt 3, H 2 is activated in a stepwise manner; for the "less frustrated" Ar F 2BH/DABCO, H 2 is activated in a concerted fashion (see scheme). © 2011 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.

引用

页码：12227 / 12231

页数：5

共 53 条

[1]

Alcarazo M., 2010, ANGEW CHEM, V122, P5924

[2] Exploring the Reactivity of Carbon(0)/Borane-Based Frustrated Lewis Pairs [J].

Alcarazo, Manuel ;

Gomez, Catherine ;

Holle, Sigrid ;

Goddard, Richard .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2010, 49 (33) :5788-5791

[3]

[Anonymous], 2008, ANGEW CHEM

[4] Crucial role of anions on the deprotonation of the cationic dihydrogen complex trans-[FeH(η2-H2)(dppe)2]+ [J].

Basallote, Manuel G. ;

Besora, Maria ;

Castillo, C. Esther ;

Fernandez-Trujillo, Maria J. ;

Lledos, Agusti ;

Maseras, Feliu ;

Manez, M. Angeles .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2007, 129 (20) :6608-6618

[5] Lewis acidity of tris(pentafluorophenyl) borane:: crystal and molecular structure of B(C6F5)3•OPEt3 [J].

Beckett, MA ;

Brassington, DS ;

Coles, SJ ;

Hursthouse, MB .

INORGANIC CHEMISTRY COMMUNICATIONS, 2000, 3 (10) :530-533

[6]

Chase P.A., 2007, Angewandte Chemie, V119, P8196, DOI DOI 10.1002/ANGE.200702908

[7]

Chase P.A., 2008, ANGEW CHEM, V120, P7543, DOI DOI 10.1002/ANGE.200802596

[8] Hydrogen and amine activation by a frustrated Lewis pair of a bulky n-heterocyclic carbene and B(C6F5)3 [J].

Chase, Preston A. ;

Stephan, Douglas W. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2008, 47 (39) :7433-7437

[9] Lewis acid-catalyzed hydrogenation:: B(C6F5)3-mediated reduction of imines and nitriles with H2 [J].

Chase, Preston A. ;

Jurca, Titel ;

Stephan, Douglas W. .

CHEMICAL COMMUNICATIONS, 2008, (14) :1701-1703

[10] Metal-free catalytic hydrogenation [J].

Chase, Preston A. ;

Welch, Gregory C. ;

Jurca, Titel ;

Stephan, Douglas W. .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2007, 46 (42) :8050-8053

← 1 2 3 4 5 6 →