Evidence that π‐ligand exchange reactions of chalcogen iranium ions proceed via Hückel pseudocoarctate transition states,Journal of Physical Organic Chemistry

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Evidence that π‐ligand exchange reactions of chalcogen iranium ions proceed via Hückel pseudocoarctate transition states
Journal of Physical Organic Chemistry ( IF 1.9 ) Pub Date : 2020-07-16 , DOI: 10.1002/poc.4111
Samuel C. Brydon ₁ , Gabriel Silva ₂ , Jonathan M. White ₁

Affiliation

Despite numerous computational and experimental studies on the π‐ligand exchange reactions of chalcogen iranium ions, a classification of the reaction class has yet to be made. The characteristics of the transition states presented thus far suggested a coarctate nature with two bonds breaking and forming simultaneously at the chalcogen centre. The change in barrier height, depending on the nature of the chalcogen and the alkene, was initially attributed as a shift in the degree of aromaticity moving from pseudocoarctate to coarctate reactions. However, this paper suggests that all 12 reactions under consideration are pseudocoarctate with a Hückel number of delocalised π electrons based on comprehensive studies of the orbital interactions and magnetic properties both at the transition state and along the reaction path. The change in barrier height was largely driven by the electrophilicity of the chalcogen and the strain present in the three‐membered ring rather than a shift in the degree of aromaticity.

中文翻译：

硫属元素铀离子的π-配体交换反应通过Hückel伪缩合物过渡态进行的证据

尽管对硫属元素镧离子的π-配体交换反应进行了大量的计算和实验研究，但尚未对反应类别进行分类。到目前为止呈现的过渡态的特征表明其缩聚性质，在硫族元素中心同时断裂并同时形成两个键。取决于硫族元素和烯烃的性质，势垒高度的变化最初归因于芳香性程度从假缩合物转变为缩缩反应的转变。然而，本文基于对过渡态和沿反应路径的轨道相互作用和磁学性质的综合研究，正在考虑的所有12个反应都是具有Hückel数量的离域π电子的伪缩合。

更新日期：2020-07-16

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