NMR spectra of salicylohydroxamic acid in DMSO-d6 solution: a DFT study

The H, C and H, C COSY NMR spectra of salicylohydroxamic acid (sha) were measured in DMSO-d6 solution. The B3LYP GIAO method with the 6-311þþG(d,p) basis set was chosen to reproduce the experimental spectra. All possible zusammen and entgegen conformers of monomeric sha were computed. After geometry optimisation (B3LYP/6311þþG(d,p)) only nine independent models of the molecule were shown to be stable. Additionally, the NMR chemical shifts of the Onsager model of the most stable monomer were calculated. The computed chemical shifts for the labile protons for all aforementioned geometries meaningfully underestimated experimental results suggesting the existence of the H-bonded structure of sha in DMSO solution. The most probable two dimeric structures along with two solvent-bounded aggregates were subsequently calculated at the same level of theory. The best agreement was obtained for sha H-bonded with two DMSO molecules (confirmed by the absence of concentration effect). The relative error not exceeding 10 and 4% for chemical shifts in H and C NMR spectra of sha–(DMSO)2, respectively, showed that the applied method with the B3LYP/6-311þþG(d,p) basis set was efficient to predict the NMR shifts of a compound with strong H-bonds. Thus, this allows to assign properly NMR resonances to specific structure formed in DMSO solution. q 2003 Elsevier B.V. All rights reserved.