Solvent polarity and hydrogen-bonding effects on the nitrogen NMR shieldings of N-nitrosamines and DFT calculations of the shieldings of C-, N-, and O-nitroso systems

• Published in: Journal of magnetic resonance (1997) 2003-10, Vol.164 (2), p.212-219
• Main Authors: Witanowski, Michal, Biedrzycka, Zenobia, Sicinska, Wanda, Grabowski, Zbigniew
• Format: Article
• Language: English
• Subjects: 14N NMR; Algorithms; Binding Sites; Calculations; Carbon - chemistry; Computer Simulation; Density functional theory; Hydrogen Bonding; Macromolecular Substances; Magnetic Resonance Spectroscopy - methods; Models, Molecular; Molecular Conformation; Molecular Structure; Nitrogen - chemistry; Nitrogen chemical shifts; Nitrogen Isotopes - chemistry; Nitrogen shieldings; Nitrosamines; Nitrosamines - chemistry; Nitroso Compounds - chemistry; Nitroso groups; Oxygen - chemistry; Solutions; Solvent effects; Solvents - chemistry
• ISSN: 1090-7807; 1096-0856
• DOI: 10.1016/S1090-7807(03)00267-2

High-precision nitrogen NMR shieldings, bulk susceptibility corrected, are reported for dimethyl- N-nitrosamine ( I) and diethyl- N-nitrosamine ( II) in a variety of solvents which represent a wide range of solvent properties from the point of view of polarity as well as hydrogen bond donor and acceptor strength. The observed range of solvent-induced nitrogen shielding variations of ( I) and ( II) is significant for the amino-type nitrogens, up to about 16 ppm, and originates essentially from the deshielding effect of the increasing polarity of solvent. On the other side, the nitroso nitrogen shieldings reveal an even stronger response to solvent effects, within about 20 ppm, but in this case the increasing polarity and hydrogen bond donor strength of solvent produce enhanced shielding. DFT quantum-mechanical calculations using the GIAO/B3PW91/6-311++G** approach and geometry optimizations employing the same basis set and hybrid density functionals show an excellent correlation with the experimental data on C-, N-, and O-nitroso moieties and reproduce not only major changes but also most of the subtle variations in the experimental nitrogen shieldings of the nitroso systems as a whole. A combination of the calculations involving the corresponding N and O-protonated species and the trends observed in the solvent-induced nitrogen shielding variations shows clearly that the prime acceptor site for hydrogen bonding is the nitroso oxygen atom.