Accessible Unlicensed Requires Authentication Published by Oldenbourg Wissenschaftsverlag June 10, 2013

Competition between Hydrogen Bonds and Lewis Acid-Base Interactions in the Equilibria between Bis(pentafluorophenyl)borinic Acid and Pyridine: Insights from NMR, Diffractometric and Computational Studies

Daniela Maggioni, Tiziana Beringhelli, Guiseppe D' Alfonso, Maria Carlotta Malatesta, Pierluigi Mercandelli and Daniela Donghi

Abstract

1H and 19F NMR spectroscopy, X-ray diffractometry and DFT computations have been used for investigating the interaction between the Lewis base pyridine and bis(pentafluorophenyl)borinic acid Ar2BOH (1, Ar=C6F5). Previous studies showed that the latter species in solution exists as an equilibrium mixture of the monomer (1m) and a cyclic trimer (1t), in variable ratios, and that the trimer is stabilized in the presence of Lewis bases, by the formation of strong 1t···L hydrogen bonds. In the present case, upon addition of 0.33 equivalents of pyridine, low-temperature NMR spectra showed the formation of deprotonated 1t (anion 3), strongly hydrogen-bonded to the pyridinium cation Hpy+. The presence of this cation was confirmed by the high value of 1JHN (88 Hz). DFT computations confirmed the higher stability of the O-···H–N+ limit form over the neutral O–H···N one. Variable temperature NMR spectra showed that the Hpy+·3 ion pair has high conformational freedom. At temperatures higher than 260 K, 3 underwent reversible partial fragmentation to give 1m and the Lewis acid-base covalent adducts between pyridine and either 1m (2py), or its anhydride (5py). The fragmentation was perfectly reversible on lowering the temperature. The adduct 2py became the only species in solution in the presence of 1 equivalent of pyridine, showing that the Lewis basicity of pyridine plays the major role, at variance with what previously observed with other bases. Hydrogen bond interactions, however, promote the supramolecular organization of 2py in the form of a cyclic tetramer, as revealed by X-ray single crystal diffractometric analysis. The formation of the deprotonated trimer 3 was previously observed in the reaction of 1 with 1,8-bis(dimethylamino)naphtalene (DMAN). However the stepwise dearylation processes, which were dominant in the reactions with DMAN, have a very marginal role in the reaction with pyridine, due to its lower Brønsted basicity.

For Supplementary Material see online version. Supporting information available: details of the NMR spectroscopic characterization (Figs. S1–S4), computed chemical shifts (Table S1), details of the X-ray diffractometric analysis, and tables of geometrical parameters (Tables S2–S3).


* Correspondence address: University of Zurich, Institute of Inorganic Chemistry, Winterthurerstrasse 190, CH-8057 Zurich, Schweiz,

Published Online: 2013-6-10
Published in Print: 2013-6-1

© by Oldenbourg Wissenschaftsverlag, München, Germany