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Solid‐state 11B and 13C NMR,IR, and X‐ray crystallographic characterization of selected arylboronic acids and their catechol cyclic esters
Authors:Se‐Woung Oh  Joseph W. E. Weiss  Phillip A. Kerneghan  Ilia Korobkov  Kenneth E. Maly  David L. Bryce
Affiliation:1. Department of Chemistry, University of Ottawa, , Ottawa, ON, Canada;2. On leave from the Department of Chemistry, Mokpo National University, , Muan, Chonnam, Korea;3. Department of Chemistry, Wilfrid Laurier University, , Waterloo, ON, Canada
Abstract:Nine arylboronic acids, seven arylboronic catechol cyclic esters, and two trimeric arylboronic anhydrides (boroxines) are investigated using 11B solid‐state NMR spectroscopy at three different magnetic field strengths (9.4, 11.7, and 21.1 T). Through the analysis of spectra of static and magic‐angle spinning samples, the 11B electric field gradient and chemical shift tensors are determined. The effects of relaxation anisotropy and nutation field strength on the 11B NMR line shapes are investigated. Infrared spectroscopy was also used to help identify peaks in the NMR spectra as being due to the anhydride form in some of the arylboronic acid samples. Seven new X‐ray crystallographic structures are reported. Calculations of the 11B NMR parameters are performed using cluster model and periodic gauge‐including projector‐augmented wave (GIPAW) density functional theory (DFT) approaches, and the results are compared with the experimental values. Carbon‐13 solid‐state NMR experiments and spectral simulations are applied to determine the chemical shifts of the ipso carbons of the samples. One bond indirect 13C‐11B spin‐spin (J) coupling constants are also measured experimentally and compared with calculated values. The 11B/10B isotope effect on the 13C chemical shift of the ipso carbons of arylboronic acids and their catechol esters, as well as residual dipolar coupling, is discussed. Overall, this combined X‐ray, NMR, IR, and computational study provides valuable new insights into the relationship between NMR parameters and the structure of boronic acids and esters. Copyright © 2012 John Wiley & Sons, Ltd.
Keywords:nuclear magnetic resonance  solid‐state NMR  boron‐11  carbon‐13  boronic acids  boronate esters  relaxation anisotropy  isotope effects  quadrupolar coupling constant  chemical shift tensor
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