1H NMR spectra of ethane‐1, 2‐diol and other vicinal diols in benzene: GIAO/DFT shift calculations. (20th November 2012)

• Record Type: Journal Article
• Authors: Lomas, John S.
• Is Part Of: Magnetic resonance in chemistry. Volume 51:Number 1(2013:Jan.)
• Page Start: 32
• Page End: 41
• Publication Date: 2012-11-20
• Subjects: Nuclear magnetic resonance spectroscopy -- Periodicals; Chemistry, Organic -- Periodicals; Magnetic resonance -- Periodicals; 538.36
• DOI: 10.1002/mrc.3899
• Languages: English
• ISSNs: 0749-1581

Abstract

<abstract abstract-type="main"> <title> <x xml:space="preserve">Abstract</x> </title> <p>The proton NMR spectra of several 1, 2‐diols in benzene have been analysed so as to associate each magnetically nonequivalent proton with its chemical shift. The shifts and coupling constants of the OH and methylene protons of ethane‐1, 2‐diol have been determined in a wide range of solvents. The conformer distribution and the proton NMR shifts of these 1, 2‐diols in benzene have been computed on the basis of density functional theory. The solvent is included using the integral–equation–formalism polarizable continuum model implemented in Gaussian 09. Relative Gibbs energies for all stable conformers are calculated at the Perdew, Burke and Enzerhof (PBE)0/6‐311 + G(d, p) level, and shifts are calculated using the gauge‐including atomic orbital method with the PBE0/6‐311 + G(d, p) geometry but using the cc‐pVTZ basis set. Previous calculations on ethane‐1, 2‐diol and propane‐1, 2‐diol have been corrected and extended. New calculations on <italic>tert</italic>‐butylethane‐1, 2‐diol, phenylethane‐1, 2‐diol, butane‐2, 3‐diols (<italic>dl</italic> and <italic>meso</italic>) and cyclohexane‐1, 2‐diols (<italic>cis</italic> and <italic>trans</italic>) are presented. Overall, the computed NMR shifts are in good agreement with experimental values for the OH protons but remain systematically high for CH protons. Some results based on the Gaussian 03 solvation model are included for comparison. Copyright © 2012 John Wiley & Sons, Ltd.</p> </abstract>