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Solution equilibria of aromatic dinitroso compounds: a combined NMR and DFT study

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Abstract

Solution-state nitroso monomer-azodioxide equilibria and conformational freedom of several aromatic dinitroso derivatives, differing in the spacer group between the aromatic rings, were studied by one- and two-dimensional variable temperature 1H NMR spectroscopy and by quantum chemical calculations. The proton signals of nitroso monomer-azodioxide mixtures revealed by low-temperature NMR were assigned and validated using B3LYP-D3/6-311+G(2d,p)/SMD level of theory. In almost all cases, a preference towards the formation of only one azodioxy isomer of aromatic dinitroso compounds was found, which was assigned to Z-dimer according to computational data. Nevertheless, the computed small energy difference between the Z- and E-isomer could not account for the extreme preference for Z-dimer formation, indicating an influence of entropic or solvent effects. The formation of shorter oligomers in solution was excluded based on integrated 1H NMR signal intensities. The experimental results indicated an average dimerization Gibbs energy of about − 5 kJ/mol at 223 K and were found to be in very good correlation with dimerization energies obtained by solution-phase optimization.

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Acknowledgments

This work was supported by the Croatian Science Foundation (grant no. 7444, project ORGMOL).

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Correspondence to Hrvoj Vančik or Ivana Biljan.

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The authors declare that they have no conflict of interest.

Electronic supplementary material

Supplementary materials

Optimized geometries of all compounds are supplied in .xyz format. 1H NMR, COSY and IR spectra of compounds are also provided. (DOCX 918 kb)

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Rončević, I., Bibulić, P., Vančik, H. et al. Solution equilibria of aromatic dinitroso compounds: a combined NMR and DFT study. Struct Chem 29, 1489–1497 (2018). https://doi.org/10.1007/s11224-018-1136-y

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Keywords

  • Equilibrium
  • Solution
  • Aromatic dinitroso compounds
  • Dimerization
  • NMR
  • DFT