From B(C6F5)3 to B(OC6F5)3:: Synthesis of (C6F5)2BOC6F5 and C6F5B(OC6F5)2 and their relative lewis acidity

被引:145
作者
Britovsek, GJP [1 ]
Ugolotti, J [1 ]
White, AJP [1 ]
机构
[1] Univ London Imperial Coll Sci Technol & Med, Dept Chem, London SW7 2AY, England
基金
美国海洋和大气管理局;
关键词
D O I
10.1021/om049091p
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
The pentafluorophenyl esters of bis(pentafluorophenyl)borinic acid (C6F5)(2)BOC6F5 (2) and pentafluorophenylboronic acid C6F5B(OC6F5)(2) (3) have been prepared and characterized by multinuclear NMR and X-ray analysis. VT NMR studies have shown that restricted rotation around the B-O bond in 2 occurs below 193 K, corresponding to Delta G(not equal) = 35 kJ/mol for this process. This low barrier and the random torsion angles around the B-O bonds observed in the solid state structures of compounds 2, 3, and B(OC6F5)(3) (4) suggest that these torsion angles are not related to p pi-p pi interactions between boron and oxygen, but more likely a consequence of the extensive intermolecular F-pi interactions seen in the solid state structures. The Lewis acidity of 2, 3, and 4 has been compared with B(C6F5)(3) (1), using various Lewis bases. All compounds 1-4 appear to be strong Lewis acids, whereby 4 interacts more strongly with hard bases whereas 1 binds more strongly to softer bases.
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页码:1685 / 1691
页数:7
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共 61 条
[1]   BARRIERS TO ROTATION ABOUT THE B-X BONDS OF COORDINATIVELY UNSATURATED BORATES AND THIOBORATES R2BXR' (X =O, S) ARE NOT MEASURES OF THE RELATIVE STRENGTHS OF THEIR B=O AND B=S PI BONDS [J].
ASHBY, MT ;
SHESHTAWY, NA .
ORGANOMETALLICS, 1994, 13 (01) :236-243
[2]   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
[3]   Organophosphoryl adducts of tris(pentafluorophenyl)borane;: crystal and molecular structure of B(C6F5)3•Ph3PO [J].
Beckett, MA ;
Brassington, DS ;
Light, ME ;
Hursthouse, MB .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 2001, (11) :1768-1772
[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]   Aqua, alcohol, and acetonitrile adducts of tris(perfluorophenyl)borane: Evaluation of Bronsted acidity and ligand lability with experimental and computational methods [J].
Bergquist, C ;
Bridgewater, BM ;
Harlan, CJ ;
Norton, JR ;
Friesner, RA ;
Parkin, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2000, 122 (43) :10581-10590
[6]   The role of water in the oligomerization equilibria involving bis(pentafluorophenyl)borinic acid in dichloromethane solution [J].
Beringhelli, T ;
D'Alfonso, G ;
Donghi, D ;
Maggioni, D ;
Mercandelli, P ;
Sironi, A .
ORGANOMETALLICS, 2004, 23 (23) :5493-5502
[7]   Bis(pentafluorophenyl)borinic acid: a cyclic trimer in the solid state and a monomer, with hindered rotation around the B-OH bond, in solution [J].
Beringhelli, T ;
D'Alfonso, G ;
Donghi, D ;
Maggioni, D ;
Mercandelli, P ;
Sironi, A .
ORGANOMETALLICS, 2003, 22 (08) :1588-1590
[8]   1H and 19F NMR investigation of the reaction of B(C6F5)3 with water in toluene solution [J].
Beringhelli, T ;
Maggioni, D ;
D'Alfonso, G .
ORGANOMETALLICS, 2001, 20 (23) :4927-4938
[9]   Role of B(C6F5)3 in catalyst activation, anion formation, and as C6F5 transfer agent [J].
Bochmann, M ;
Lancaster, SJ ;
Hannant, MD ;
Rodriguez, A ;
Schormann, M ;
Walker, DA ;
Woodman, TJ .
PURE AND APPLIED CHEMISTRY, 2003, 75 (09) :1183-1195
[10]   Reversible adduct formation between phosphines and triarylboron compounds [J].
Bradley, DC ;
Harding, IS ;
Keefe, AD ;
Motevalli, M ;
Zheng, DH .
JOURNAL OF THE CHEMICAL SOCIETY-DALTON TRANSACTIONS, 1996, (20) :3931-3936