Insights into the insertion reaction mechanism of phosphenium cation and oxirane: a theoretical study

IF 1.7 4区化学 Q3 Chemistry

Journal of Chemical Sciences Pub Date : 2022-04-27 DOI:10.1007/s12039-022-02057-x

Xiaojun Tan, Yingxin Mao, Guizhi Shi, Huilian Xu, Yan He, Jinsong Gu

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Abstract

The mechanism of insertion reaction between phosphenium cation and phosphindene with oxirane has been investigated theoretically to better understand the reactivity for the valence isoelectronic of carbene. Phosphenium cation acts as an electrophilic reagent and accepts σ electrons of oxirane to form a complex in the first combination step. The greater the positive charge on phosphorus in phosphenium cation, the more stable the formed complex is. The introduction of substituents will decrease the positive charge on phosphorus in phosphenium cation. The order of positive charge on phosphorus is HP⁺-F > HP⁺-OH > HP⁺-NH₂, which is consistent with their Lewis acidities. The complex transforms to a four-membered ring product via a transition state in the second insertion step. The product is more stable than the complex due to the decrease of ring extension.

Graphical abstract

Phosphenium cation acts as an electrophilic reagent and accepts σ electrons of oxygen in oxirane to form a four-membered ring product. The introduction of substituents will decrease the positive charge on phosphorus in phosphenium cation, which reduced the stability of the products.

Abstract Image

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磷阳离子与氧环烷插入反应机理的理论研究

从理论上研究了磷阳离子与膦烯与氧环烷插入反应的机理，以便更好地了解碳烯价电子等电子的反应性。磷离子作为亲电试剂，在第一步结合过程中接受氧环烷的σ电子形成络合物。磷阳离子中磷的正电荷越大，形成的络合物越稳定。取代基的引入会使磷离子上的正电荷减少。磷的正电荷顺序为HP+-F >惠普+ -哦比;HP+-NH2，这与它们的路易斯酸相一致。在第二插入步骤中，该配合物通过过渡态转变为四元环产物。由于减少了环的延伸，产物比络合物更稳定。图示:阳离子磷作为亲电试剂，接受氧的σ电子形成四元环产物。取代基的引入会降低磷离子中磷的正电荷，从而降低产物的稳定性。

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来源期刊

Journal of Chemical Sciences Chemistry-General Chemistry

CiteScore

2.90

自引率

5.90%

发文量

107

审稿时长

12 months

期刊介绍： Journal of Chemical Sciences is a monthly journal published by the Indian Academy of Sciences. It formed part of the original Proceedings of the Indian Academy of Sciences – Part A, started by the Nobel Laureate Prof C V Raman in 1934, that was split in 1978 into three separate journals. It was renamed as Journal of Chemical Sciences in 2004. The journal publishes original research articles and rapid communications, covering all areas of chemical sciences. A significant feature of the journal is its special issues, brought out from time to time, devoted to conference symposia/proceedings in frontier areas of the subject, held not only in India but also in other countries.