A Phosphorus/Aluminum-Based Frustrated Lewis Pair as an Ion Pair Receptor: Alkali Metal Hydride Adducts and Phase-Transfer Catalysis

被引:93
作者
Appelt, Christian [2 ]
Slootweg, J. Chris [1 ]
Lammertsma, Koop [1 ]
Uhl, Werner [2 ]
机构
[1] Vrije Univ Amsterdam, Dept Chem & Pharmaceut Sci, NL-1081 HV Amsterdam, Netherlands
[2] Univ Munster, Inst Anorgan & Analyt Chem, D-48149 Munster, Germany
关键词
alkali metals; density functional calculations; frustrated Lewis pairs; hydrides; silanes; COMPLEX REDUCING AGENTS; REDUCTION REACTIONS; CRYSTAL-STRUCTURES; LITHIUM HYDRIDE; COORDINATION; ACTIVATION; HYDROGENATION; DERIVATIVES; REAGENTS; LIGANDS;
D O I
10.1002/anie.201201855
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Helpful frustration: The geminal phosphorus/aluminum-based frustrated Lewis pair (Mes 2P)(tBu 2Al)C-C(H)Ph (Mes=2,4,6-Me 3C 6H 2) forms stable adducts with alkali metal hydrides (LiH, NaH, KH). These molecular hydride complexes display enhanced reactivity, which was demonstrated by the catalytic transformation of chlorotriphenylsilane to the corresponding hydride through a frontside S N2-f@Si pathway. Copyright © 2012 WILEY-VCH Verlag GmbH & Co. KGaA, Weinheim.
引用
收藏
页码:5911 / 5914
页数:4
相关论文
共 70 条
[1]   Hydrides of the main-group metals: New variations on an old theme [J].
Aldridge, S ;
Downs, AJ .
CHEMICAL REVIEWS, 2001, 101 (11) :3305-3365
[2]  
[Anonymous], 2009, ANGEW CHEM
[3]  
Appelt C., 2011, Angew. Chem, V123, P4011
[4]   Geminal Phosphorus/Aluminum-Based Frustrated Lewis Pairs: C-H versus C≡C Activation and CO2 Fixation [J].
Appelt, Christian ;
Westenberg, Hauke ;
Bertini, Federica ;
Ehlers, Andreas W. ;
Slootweg, J. Chris ;
Lammertsma, Koop ;
Uhl, Werner .
ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2011, 50 (17) :3925-3928
[5]   A 1,1′-ferrocenyl phosphine-borane: synthesis, structure and evaluation in Rh-catalyzed hydroformylation [J].
Bebbington, Magnus W. P. ;
Bontemps, Sebastien ;
Bouhadir, Ghenwa ;
Hanton, Martin J. ;
Tooze, Robert P. ;
van Rensburg, Hendrick ;
Bourissou, Didier .
NEW JOURNAL OF CHEMISTRY, 2010, 34 (08) :1556-1559
[6]   Frontside versus Backside SN2 Substitution at Group 14 Atoms: Origin of Reaction Barriers and Reasons for Their Absence [J].
Bento, A. Patricia ;
Bickelhaupt, F. Matthias .
CHEMISTRY-AN ASIAN JOURNAL, 2008, 3 (10) :1783-1792
[7]   Nucleophilic substitution at silicon (SN2@Si) via a central reaction barrier [J].
Bento, A. Patricia ;
Bickelhaupt, F. Matthias .
JOURNAL OF ORGANIC CHEMISTRY, 2007, 72 (06) :2201-2207
[8]   Tandem Frustrated Lewis Pair/Tris(pentafluorophenyl)borane-Catalyzed Deoxygenative Hydrosilylation of Carbon Dioxide [J].
Berkefeld, Andreas ;
Piers, Warren E. ;
Parvez, Masood .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2010, 132 (31) :10660-10661
[9]   B(C6F5)3-catalyzed hydrosilation of imines via silyliminium intermediates [J].
Blackwell, JM ;
Sonmor, ER ;
Scoccitti, T ;
Piers, WE .
ORGANIC LETTERS, 2000, 2 (24) :3921-3923
[10]   POTASSIUM HYDRIDE, A HIGHLY ACTIVE NEW HYDRIDE REAGENT - REACTIVITY, APPLICATIONS, AND TECHNIQUES IN ORGANIC AND ORGANOMETALLIC REACTIONS [J].
BROWN, CA .
JOURNAL OF ORGANIC CHEMISTRY, 1974, 39 (26) :3913-3918