Journal of the Iranian Chemical Society

, Volume 11, Issue 1, pp 17–25

Intramolecular interactions in nitroamines studied by 1H, 13C, 15N and 17O NMR spectral and quantum chemical methods

  • Ryszard Gawinecki
  • Erkki Kolehmainen
  • Robert Dobosz
  • Hossein Loghmani Khouzani
  • Subramanian Chandrasekaran
Original Paper

DOI: 10.1007/s13738-013-0269-6

Cite this article as:
Gawinecki, R., Kolehmainen, E., Dobosz, R. et al. J IRAN CHEM SOC (2014) 11: 17. doi:10.1007/s13738-013-0269-6

Abstract

1H, 13C, 15N and 17O NMR chemical shifts are used for the characterization of the intramolecular interactions in several nitramines of the Me2N-G-NO2 type. The charge of lone electron pair of the amino group in N,N-dimethylnitramine, N,N-dimethyl-2-nitroethenamine, N,N-dimethyl-p-nitroaniline, 4-nitro-β-dimethylaminostyrene, 4-N,N-dimethylamino-β-nitrostyrene, 4-(N,N-dimethylamino)-4′-nitrobiphenyl, and 4-(N,N-dimethylamino)-4′-nitrostilbene is transferred not only to the nitro oxygens, but also to the vinylene and benzene carbons of the G spacer and to N-methyl carbons as well. Decreased nuclear shielding is found to be qualitatively related to the decreased atomic charge around a nucleus. This finding was further verified and quantified by comparison of the NMR data with those obtained by ab initio quantum chemical calculations. 17O NMR chemical shift changes seem to be more significant when the interacting NMe2 and NO2 groups are separated by a short spacer. On the other hand, 15N NMR chemical shifts suggest that a decrease of the charge at the amino nitrogen is not related to the length of the spacer alone. A lack of the linear dependence between the 17Onitro and 15Namino chemical shifts suggests that the charge lost by the amino nitrogen was only partially gained by the oxygens in the nitro group. The increased shieldings of the aryl carbons in 4-(N,N-dimethylamino)-4′-nitrobiphenyl indicate that atoms of the p,p-biphenylene spacer also gain some charge originating from the amino nitrogen. 3JH,H spin–spin coupling constant shows that among different vinylene compounds, the charge transfer to the nitro group is practically effective only in N,N-dimethyl-2-nitroethenamine where the bond between the vinylene carbons is significantly of low order by character. The calculated Natural Population Analysis (NPA) data confirms that except the nitro oxygens, other atoms that receive the negative charge lost by NMe2 in the compounds studied are the aryl and N-methyl carbons.

Keywords

NitroaminesResonance interactionCharge transferMolecular structureAb initio calculations

Supplementary material

13738_2013_269_MOESM1_ESM.docx (27 kb)
Supplementary material 1 (DOCX 27 kb)

Copyright information

© Iranian Chemical Society 2013

Authors and Affiliations

  • Ryszard Gawinecki
    • 1
  • Erkki Kolehmainen
    • 2
  • Robert Dobosz
    • 1
  • Hossein Loghmani Khouzani
    • 3
  • Subramanian Chandrasekaran
    • 4
  1. 1.Department of ChemistryUniversity of Technology and Life SciencesBydgoszczPoland
  2. 2.Department of ChemistryUniversity of JyväskyläJyväskyläFinland
  3. 3.Department of Chemistry, Faculty of SciencesUniversity of IsfahanIsfahanIran
  4. 4.Department of ChemistryGeorgia State UniversityAtlantaUSA