Structure and Dynamic Features of an Intramolecular Frustrated Lewis Pair

被引:90
作者
Axenov, Kirill V. [1 ]
Moemming, Cornelia M. [1 ]
Kehr, Gerald [1 ]
Froehlich, Roland [1 ]
Erker, Gerhard [1 ]
机构
[1] Univ Munster, Inst Organ Chem, D-48149 Munster, Germany
关键词
boron; frustrated Lewis pairs; hydrogen; phosphorus; FREE CATALYTIC-HYDROGENATION; HETEROLYTIC DIHYDROGEN ACTIVATION; METAL-FREE; BORANE; REACTIVITY; IMINES; H-2; BIS(PENTAFLUOROPHENYL)BORANE; PHOSPHINES; REDUCTION;
D O I
10.1002/chem.201001814
中图分类号
O6 [化学];
学科分类号
0703 ;
摘要
Di(mesityl)cyclohexenylphosphine undergoes hydroboration with Piers' borane [HB(C6F5)(2)] to yield the cyclohexylene-anellated frustrated Lewis pair 5. This P/B pair splits H-2 with the formation of the product 4 and adds to the C=O double bond of phenyl isocyanate to yield 6. In the crystal, compound 5 features a puckered four-membered heterocyclic core structure with a long P B bond (ay. 2.197(5) angstrom). The activation energy of the P B cleavage of the frustrated Lewis pair 5 was determined by dynamic F-19 NMR spectroscopy at Delta G(not equal) (298 K) = 12.1 +/- 0.3 kcal mol(-1).
引用
收藏
页码:14069 / 14073
页数:5
相关论文
共 74 条
[11]  
Chase P.A., 2007, Angewandte Chemie, V119, P8196, DOI DOI 10.1002/ANGE.200702908
[12]  
Chase P.A., 2008, ANGEW CHEM, V120, P7543, DOI DOI 10.1002/ANGE.200802596
[13]   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
[14]   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
[15]   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
[16]   Frustrated Lewis pairs derived from N-heterocyclic carbenes and Lewis acids [J].
Chase, Preston A. ;
Gille, Austin L. ;
Gilbert, Thomas M. ;
Stephan, Douglas W. .
DALTON TRANSACTIONS, 2009, (35) :7179-7188
[17]   Remarkably variable reaction modes of frustrated Lewis pairs with non-conjugated terminal diacetylenes [J].
Chen, Chao ;
Froehlich, Roland ;
Kehr, Gerald ;
Erker, Gerhard .
CHEMICAL COMMUNICATIONS, 2010, 46 (20) :3580-3582
[18]   Metal-free catalytic hydrogenation of imines with tris(perfluorophenyl) borane [J].
Chen, Dianjun ;
Klankermayer, Juergen .
CHEMICAL COMMUNICATIONS, 2008, (18) :2130-2131
[19]   Activation of H2 by phosphinoboranes R2PB(C6F5)2 [J].
Geier, Stephen J. ;
Gilbert, Thomas M. ;
Stephan, Douglas W. .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2008, 130 (38) :12632-+
[20]   New Strategies to Phosphino-Phosphonium Cations and Zwitterions [J].
Geier, Stephen J. ;
Dureen, Meghan A. ;
Ouyang, Eva Y. ;
Stephan, Douglas W. .
CHEMISTRY-A EUROPEAN JOURNAL, 2010, 16 (03) :988-993