Solution structure, dynamics and speciation of perfluoroaryl boranes through 1H, 11B and 19F NMR spectroscopy

被引:88
作者
Beringhelli, Tiziana [1 ]
Donghi, Daniela [1 ]
Maggioni, Daniela [1 ]
D'Alfonso, Giuseppe [1 ]
机构
[1] Univ Milan, Dipartimento Chim Inorgan Metallorgan & Analit, I-20133 Milan, Italy
关键词
Perfluoroaryl boranes; NMR spectroscopy; Lewis acids; Hydrogen bonds; Dynamical behaviour;
D O I
10.1016/j.ccr.2008.01.018
中图分类号
O61 [无机化学];
学科分类号
070301 ; 081704 ;
摘要
Multinuclear NMR spectroscopy has been used to study the solution properties of several perfluoroaryl borane derivatives. The information obtained from all the NMR active isotopes present in these molecules made it possible to establish not only chemical identity, structure and dynamics of their reaction products, but also the complexity of the solution speciation. In other words, multinuclear NMR helped in unravelling the real forms in which they are present in solution, that in some cases can change dramatically according to even slight changes of the solution conditions. Examples will be presented related to the chemistry of tris(pentafluorophenyl)borane, B(C6F5)(3), and bis(pentafluorophenyl)borinic acid, B(C6F5)(2)OH. (C) 2008 Elsevier B.V. All rights reserved.
引用
收藏
页码:2292 / 2313
页数:22
相关论文
共 115 条
[1]   HYDROGEN-BONDING .10. A SCALE OF SOLUTE HYDROGEN-BOND BASICITY USING LOG K VALUES FOR COMPLEXATION IN TETRACHLOROMETHANE [J].
ABRAHAM, MH ;
GRELLIER, PL ;
PRIOR, DV ;
MORRIS, JJ ;
TAYLOR, PJ .
JOURNAL OF THE CHEMICAL SOCIETY-PERKIN TRANSACTIONS 2, 1990, (04) :521-529
[2]   Displacement of weakly coordinating anions from zirconocene alkyl cations by trialkyl phosphines: A model for olefin coordination in homogeneous Ziegler-Natta catalysis [J].
Beck, S ;
Prosenc, MH ;
Brintzinger, HH .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1998, 128 (1-3) :41-52
[3]   Anion exchange in alkyl-zirconocene borate ion pairs. Are solvated alkyl-zirconocene cations relevant intermediates? [J].
Beck, S ;
Lieber, S ;
Schaper, F ;
Geyer, A ;
Brintzinger, HH .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2001, 123 (07) :1483-1489
[4]   Binuclear zirconocene cations with mu-CH3-bridges in homogeneous Ziegler-Natta catalyst systems [J].
Beck, S ;
Prosenc, MH ;
Brintzinger, HH ;
Goretzki, R ;
Herfert, N ;
Fink, G .
JOURNAL OF MOLECULAR CATALYSIS A-CHEMICAL, 1996, 111 (1-2) :67-79
[5]   Diverse world of unconventional hydrogen bonds [J].
Belkova, NV ;
Shubina, ES ;
Epstein, LM .
ACCOUNTS OF CHEMICAL RESEARCH, 2005, 38 (08) :624-631
[6]   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
[7]   Protonation of the hydroxide ligand in a synthetic analogue of carbonic anhydrase, [TpBut,Me]ZnOH:: inhibition of reactivity towards CO2 [J].
Bergquist, C ;
Parkin, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 1999, 121 (26) :6322-6323
[8]   Protonation and reactivity towards carbon dioxide of the mononuclear tetrahedral zinc and cobalt hydroxide complexes, [TpBut,Me]ZnOH and [TpBut,Me]CoOH:: Comparison of the reactivity of the metal hydroxide function in synthetic analogues of carbonic anhydrase [J].
Bergquist, C ;
Fillebeen, T ;
Morlok, MM ;
Parkin, G .
JOURNAL OF THE AMERICAN CHEMICAL SOCIETY, 2003, 125 (20) :6189-6199
[9]   Solution conformation and dynamics of the ion pairs originating from the reaction of B(C6F5)3 with bisindenyl dimethyl zirconium complexes [J].
Beringhelli, T ;
D'Alfonso, G ;
Maggioni, D ;
Mercandelli, P ;
Sironi, A .
CHEMISTRY-A EUROPEAN JOURNAL, 2005, 11 (02) :650-661
[10]   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