Title |
Can Variations of 1H NMR Chemical Shifts in Benzene Substituted with an Electron‐Accepting (NO2)/Donating (NH2) Group be Explained in Terms of Resonance Effects of Substituents?
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Published in |
Chemistry - An Asian Journal, March 2018
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DOI | 10.1002/asia.201800137 |
Pubmed ID | |
Authors |
Marija Baranac‐Stojanović |
Abstract |
The classical textbook explanation of variations of 1 H NMR chemical shifts in benzenes bearing an electron-donating (NH2 ) or an electron-withdrawing (NO2 ) group in terms of substituent resonance effects was examined by analyzing molecular orbital contributions to the total shielding. It was found that the π-electronic system showed a more pronounced shielding effect on all ring hydrogen atoms, relative to benzene, irrespective of substituent +R/-R effects. For the latter, this was in contrast to the traditional explanations of downfield shift of nitrobenzene proton resonances, which were found to be determined by the σ-electronic system and oxygen in-plane lone pairs. In aniline, the +R effect of NH2 group can be used to fully explain the upfield position of meta-H signals and partly the upfield position of para-H signals, the latter also being influenced by the σ-system. The position of the lowest frequency signal of ortho-Hs was fully determined by σ-electrons. |
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