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Chemical Reactivity Controlled by Negative Hyperconjugation:A Theoretical Study

机译:负超共轭控制化学反应性的理论研究

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Negative hyperconjugation is a general phenomenon that can be observed in many areas of chemistry The knowledge of its impact on structural parameters and conformational issues is well established but little is known about its importance for chemical reactivity Here we present a system activ study of different aspects of negative hyperconjugation on the reactivity of complex heterocyclic systems using density functional theory Intermediates drom the reaction of nitrogen-based nucleophiles with bis(1,3,4-thiadiazolo)-1,3,5-triazinium halides serve as benchmark system s to demonstrate the effects of negative hyperconjugation on bond lengths on te relative stability of conformational isomes and transition structures and most importantly on the different reaction pathways of these species The computational results provided here are in part supported by experients reported elsewhere.
机译:负超共轭反应是在化学的许多领域都可以观察到的普遍现象。其对结构参数和构象问题的影响的知识已广为人知,但对其化学反应活性的重要性了解甚少。使用密度泛函理论对复杂杂环系统的反应性进行负超共轭反应,可将基于氮的亲核试剂与双(1,3,4-噻二唑)-1,3,5-三叠氮化物卤化物的反应作为基准系统来证明负超共轭对键长的影响,对构象等位基因和过渡结构的相对稳定性的影响,最重要的是对这些物种的不同反应途径的影响。此处提供的计算结果部分受到其他地方报道的经验的支持。

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