Heterolytic activation of hydrogen using frustrated Lewis pairs containing tris(2,2′,2"-perfluorobiphenyl)borane

被引：29

作者：

Binding, Samantha C. ^{[1
]}

Zaher, Hasna ^{[1
]}

Chadwick, F. Mark ^{[1
]}

O'Hare, Dermot ^{[1
]}

机构：

[1] Univ Oxford, Inorgan Chem Lab, Oxford OX1 3QR, England

来源：

DALTON TRANSACTIONS | 2012年 / 41卷 / 30期

关键词：

FREE CATALYTIC-HYDROGENATION; X-RAY-DIFFRACTION; METAL-FREE; DIHYDROGEN ACTIVATION; CARBON-DIOXIDE; ROOM-TEMPERATURE; H-2; ACTIVATION; BORANE; REACTIVITY; B(C6F5)(3);

D O I：

10.1039/c2dt30334e

中图分类号：

O61 [无机化学];

学科分类号：

070301 ; 081704 ;

摘要：

The extremely sterically hindered borane tris(2,2',2 ''-perfluorobiphenyl)borane (PBB) has been structurally characterised. In combination with bulky nitrogen bases, it forms the 'frustrated Lewis pairs' (FLPs) PBB/2,2,6,6-tetramethylpiperidine (TMP) (1), PBB/1,4-diazobicyclo[2.2.2]-octane (DABCO) (2) and PBB/2,6-lutidine (lut) (3). These novel, unquenched acid-base pairs have been shown to effect facile room temperature heterolytic cleavage of dihydrogen to form the ammonium borate salts [2,2,6,6-Me4C5H6NH2][HB(C12F9)(3)] (4) and [N(C2H4)(3)NH][HB(C12F9)(3)] (5), and lutidinium borate [2,6-Me2C5H3NH][HB(C12F9)(3)] (6). Although these reactions are equilibria, the reverse reaction and release of hydrogen gas was not apparent at temperatures up to 120 degrees C. The relative Lewis acidity of PBB has been determined using the Gutmann-Beckett method.

引用

页码：9061 / 9066

页数：6

共 76 条

[1] SIR92 - a program for automatic solution of crystal structures by direct methods [J].

ALTOMARE, A ;

CASCARANO, G ;

GIACOVAZZO, G ;

GUAGLIARDI, A ;

BURLA, MC ;

POLIDORI, G ;

CAMALLI, M .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 1994, 27 :435-435

[2] Non-Metal-Mediated Homogeneous Hydrogenation of CO2 to CH3OH [J].

Ashley, Andrew E. ;

Thompson, Amber L. ;

O'Hare, Dermot .

ANGEWANDTE CHEMIE-INTERNATIONAL EDITION, 2009, 48 (52) :9839-9843

[3] A convenient NMR method for the measurement of Lewis acidity at boron centres: Correlation of reaction rates of Lewis acid initiated epoxide polymerizations with Lewis acidity [J].

Beckett, MA ;

Strickland, GC ;

Holland, JR ;

Varma, KS .

POLYMER, 1996, 37 (20) :4629-4631

[4] 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

[5] 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

[6] CRYSTALS version 12: software for guided crystal structure analysis [J].

Betteridge, PW ;

Carruthers, JR ;

Cooper, RI ;

Prout, K ;

Watkin, DJ .

JOURNAL OF APPLIED CRYSTALLOGRAPHY, 2003, 36 :1487-1487

[7] Frustrated Lewis Pairs and Ring-Opening of THF, Dioxane, and Thioxane [J].

Birkmann, Birgit ;

Voss, Tanja ;

Geier, Stephen J. ;

Ullrich, Matthias ;

Kehr, Gerald ;

Erker, Gerhard ;

Stephan, Douglas W. .

ORGANOMETALLICS, 2010, 29 (21) :5310-5319

[8] CONFORMATIONAL-ANALYSIS OF TRIARYLBORANES [J].

BLOUNT, JF ;

FINOCCHIARO, P ;

GUST, D ;

MISLOW, K .

JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1973, 95 (21) :7019-7029

[9] Reactivity of Lewis pairs (R2PCH2AlMe2)2 with carbon dioxide [J].

Boudreau, Josee ;

Courtemanche, Marc-Andre ;

Fontaine, Frederic-Georges .

CHEMICAL COMMUNICATIONS, 2011, 47 (39) :11131-11133

[10] From B(C6F5)3 to B(OC6F5)3:: Synthesis of (C6F5)2BOC6F5 and C6F5B(OC6F5)2 and their relative lewis acidity [J].

Britovsek, GJP ;

Ugolotti, J ;

White, AJP .

ORGANOMETALLICS, 2005, 24 (07) :1685-1691

← 1 2 3 4 5 6 7 8 →