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首页> 外文期刊>Structural Chemistry >Hyperconjugative interactions are the main responsible for the anomeric effect: a direct relationship between the hyperconjugative anomeric effect, global hardness and zero-point energy
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Hyperconjugative interactions are the main responsible for the anomeric effect: a direct relationship between the hyperconjugative anomeric effect, global hardness and zero-point energy

机译：超共轭相互作用是造成异头作用的主要原因：超共轭异头作用，整体硬度和零点能量之间存在直接关系

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The correlations between the global hardness (eta), hyperconjugative anomeric effect, Pauli exchange-type repulsions, electrostatic model associated with dipole-dipole interaction and structural parameters in 2-fluorotetrahydropyran, -thiopyran, -selenopyran (1-3) and their chloro- (4-6) and bromo-analogs (7-9) were investigated by means of the conventional and range-corrected functionals and natural bond orbital (NBO) interpretation. By deletion of the HC-exo-AE and HC-endo-AE, the equatorial conformations of compounds 1-9 become more stable than their corresponding axial forms, revealing that anomeric relationships in compounds 1-9 have the hyperconjugative anomeric effect origins while the electrostatic model associated with dipole-dipole interaction does not play a determining role on the variations of the anomeric relationships in these compounds. The anomeric relationships in compounds 1-3 have no Pauli exchange-type repulsions origin, but it has a significant impact on the conformational preferences in compounds 4-6 and 7-9. A canonical molecular orbital interpretation was conducted to investigate the correlations between the linear combinations of natural bond orbitals in the HOMOs, LUMOs and the global hardness (eta) values. There is a direct relationship between the hyperconjugative anomeric effect, global hardness (eta) and zero-point energies in compounds 1-3, 4-6 and 7-9. The harder axial conformations with the greater hyperconjugative anomeric effect and zero-point energy values are more stable than their corresponding equatorial forms.
机译：在2-氟四氢吡喃，-硫代吡喃，-硒代吡喃（1-3）和它们的氯代-吡咯烷酮中，整体硬度（eta），超共轭异头效应，保利交换型斥力，与偶极-偶极相互作用相关的静电模型和结构参数之间的相关性（4-6）和溴类似物（7-9）通过常规和范围校正的功能以及天然键轨道（NBO）解释进行了研究。通过删除HC-exo-AE和HC-endo-AE，化合物1-9的赤道构象变得比其相应的轴向形式更稳定，这表明化合物1-9中的端基异构关系具有超共轭端基异构作用，而与偶极-偶极相互作用相关的静电模型对这些化合物的端基异构关系的变化没有决定性作用。化合物1-3中的端基异构关系没有Pauli交换型排斥原点，但对化合物4-6和7-9中的构象偏好有重大影响。进行了规范的分子轨道解释，以研究HOMO，LUMO中自然键轨道的线性组合与整体硬度（η）值之间的相关性。在化合物1-3、4-6和7-9中，超共轭异头作用，整体硬度（eta）和零点能量之间存在直接关系。具有较高超共轭异头作用和零点能量值的较硬轴向构型比其相应的赤道形式更稳定。

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