1H NMR spectra of alkane‐1,3‐diols in benzene: GIAO/DFT shift calculations
作者： John S. Lomas
DOI: 10.1002/MRC.3973
关键词: Proton 、 Computational chemistry 、 Atomic orbital 、 Chemistry 、 Conformational isomerism 、 Density functional theory 、 Basis set 、 Proton NMR 、 Cis–trans isomerism 、 Solvent effects
摘要: The proton nuclear magnetic resonance (NMR) spectra of propane-1,3-diol, 2-methylpropane-1,3-diol, 2,2-dimethylpropane-1,3-diol, butane-1,3-diol, 3-methylbutane-1,3-diol, pentane-2,4-diols (dl and meso), 2-methylpentane-2,4-diol cyclohexane-1,3-diols (cis trans) in benzene have been analysed. conformer distribution the NMR shifts these diols computed on basis density functional theory, solvent being included by means integral equation formalism phase continuum model (IEFPCM) implemented Gaussian 09. Relative Gibbs energies all conformers are calculated at Perdew, Burke Ernzerhof (PBE)0/6-311 + G(d,p) level, gauge-including atomic orbital method with PBE0/6-311 + G(d,p) geometry cc-pVTZ set. Vicinal coupling constants for 1,2- 1,3-diols rationalised terms relative populations geometries. hydrogen-bonded protons individual alkane-1,n-diols show a very rough correlation OH⋯OH distances. overall CH systematically high but correlate well experimental values, gradient 1.07 ± 0.01. Some values nonequivalent methylene reversed, calculation giving enhanced anti to COH bonds. Errors OH nonsymmetrical appear be related where one or other groups is donor. results based second-order Moller–Plesset approach, Becke three-parameter Lee-Yang-Parr IEFPCM solvation 03 included. Copyright © 2013 John Wiley & Sons, Ltd.
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