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

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• 作者：Ryszard Gawinecki (1)
  Erkki Kolehmainen (2)
  Robert Dobosz (1)
  Hossein Loghmani Khouzani (3)
  Subramanian Chandrasekaran (4)
  
• 关键词：Nitroamines ; Resonance interaction ; Charge transfer ; Molecular structure ; Ab initio calculations
• 刊名：Journal of the Iranian Chemical Society
• 出版年：2014
• 出版时间：February 2014
• 年：2014
• 卷：11
• 期：1
• 页码：17-25
• 全文大小：261 KB
• 作者单位：Ryszard Gawinecki (1)
  Erkki Kolehmainen (2)
  Robert Dobosz (1)
  Hossein Loghmani Khouzani (3)
  Subramanian Chandrasekaran (4)
  
  1. Department of Chemistry, University of Technology and Life Sciences, Seminaryjna 3, 85-326, Bydgoszcz, Poland
  2. Department of Chemistry, University of Jyv?skyl?, P.O. Box 35, 40014, Jyv?skyl?, Finland
  3. Department of Chemistry, Faculty of Sciences, University of Isfahan, 81744, Isfahan, Iran
  4. Department of Chemistry, Georgia State University, P.O. Box 4098, Atlanta, GA, 30302, USA
  
• ISSN：1735-2428

文摘

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. 3 J H,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.