An NMR, IR and theoretical investigation of 1H Chemical Shifts and hydrogen bonding in phenols

The change in 1H NMR chemical shifts upon hydrogen bonding was investigated using both experimental and theoretical methods. The 1H NMR spectra of a number of phenols were recorded in CDCl3 and DMSO solvents. For phenol, 2‐ and 4‐cyanophenol and 2‐nitrophenol the OH chemical shifts were measured as a function of concentration in CDCl3. The plots were all linear with concentration, the gradients varying from 0.940 (phenol) to 7.85 (4‐cyanophenol) ppm/M because of competing inter‐ and intramolecular hydrogen bonding. Ab initio calculations of a model acetone/phenol system showed that the OH shielding was linear with the H…OC distance (R) for R < 2.1 Å with a shielding coefficient of − 7.8 ppm/Å and proportional to cos2φ where φ is the H…OCC dihedral angle. Other geometrical parameters had little effect. It was also found that the nuclear shielding profile is unrelated to the hydrogen bonding energy profile. The dependence of the OH chemical shift on the π density on the oxygen atom was determined as ca 40 ppm/π electron. This factor is similar to that for NH but four times the value for sp2 hybridized carbon atoms. The introduction of these effects into the CHARGE programme allowed the calculation of the 1H chemical shifts of the compounds studied. The CHARGE calculations were compared with those from the ACD database and from GIAO calculations. The CHARGE calculations were more accurate than other calculations both when all the shifts were considered and also when the OH shifts were excluded. The calculations from the ACD and GIAO approaches were reasonable when the OH shifts were excluded but not as good when all the shifts were considered. The poor treatment of the OH shifts in the GIAO calculations is very likely due to the lack of explicit solvent effects in these calculations. Copyright © 2007 John Wiley & Sons, Ltd.