Abstract
The density functional B3LYP method with the 6-31++G(d,p) basis set was used to investigate several N-nitroso-N′,N′-dimethylphenylurea biological molecules in MeCN solution. Geometries obtained from DFT calculation were used to perform natural bond orbital (NBO) analysis. The p characters of two nitrogen natural hybrid orbital (NHO), \(\sigma_{\mathrm{N}_{3}\mbox{\scriptsize{--}}\mathrm{N}_{2}}\) bond orbitals, increase with increasing σ p values of the substituents on the benzene, which results in a lengthening of the N3–N2 bond. The p character of the oxygen NHO \(\sigma_{\mathrm{O}_{1}\mbox{\scriptsize{--}}\mathrm{N}_{2}}\) bond orbital decreases with increasing σ p values of the substituents on the benzene, which results in a shortening of the N2=O1 bond. It is also noted that decreased occupancy of the localized \(\sigma_{\mathrm{N}_{3}\mbox{\scriptsize{--}}\mathrm{N}_{2}}\) orbital occurs in the idealized Lewis structure, or increased occupancy of \(\sigma_{\mathrm{N}_{3}\mbox{\scriptsize{--}}\mathrm{N}_{2}}^{*}\) of the non-Lewis orbital, and their subsequent impact on molecular stability and geometry (bond lengths) are also related to the resulting p character of the corresponding nitrogen NHO of the \(\sigma_{\mathrm{N}_{3}\mbox{\scriptsize{--}}\mathrm{N}_{2}}\) bond orbital. In addition, the partial charge distribution on the skeletal atoms shows that the electrostatic repulsion or attraction between atoms can give a significant contribution to the intra- and intermolecular interaction.
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Acknowledgements
We gratefully thank the National Natural Science Foundation of China (Grant 10774039) and the grants from Development Program in Science and Technology of Henan Province (No. 102300410114 and No. 112300410206), Henan University of Science and Technology for Young Scholars (No. 2009QN0032), for their support of this work.
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Zhang, RZ., Li, XH., Gong, XY. et al. PCM Study of Some N-Nitroso-N′,N′-dimethylphenylurea Biological Molecules: A Natural Bond Orbital Analysis. J Solution Chem 41, 828–839 (2012). https://doi.org/10.1007/s10953-012-9831-6
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DOI: https://doi.org/10.1007/s10953-012-9831-6