磷酸阳离子与甲醛环加成反应的理论研究

IF 1.3 4区化学 Q3 CHEMISTRY, MULTIDISCIPLINARY

Main Group Chemistry Pub Date : 2022-04-16 DOI:10.3233/mgc-220037

Jiandong Sun, Xiaojun Tan, Huilian Xu, Xiujun Zhang, Yan He, Jinsong Gu

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引用次数: 0

摘要

本文在B3LYP/6-311++G(d,p)理论水平上系统地研究了磷离子与膦烯与甲醛的环加成反应机理，以便更好地了解其价电子等电子的反应性。阳离子磷作为亲电试剂，在第一步加成过程中接受甲醛的σ电子形成络合物。磷离子中磷原子的正电荷越大，形成的络合物越稳定。取代基的引入使磷原子的正电荷减少。磷原子的正电荷顺序为HP+ -F > HP+ -OH > HP+ -NH2，这与它们的路易斯酸相一致。该配合物在第二环化步骤中通过过渡态转变为三元环产物。由于产品的张力较小，因此其稳定性不如配合物。

本文章由计算机程序翻译，如有差异，请以英文原文为准。

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Theoretical study on the cycloaddition reaction of phosphenium cation and formaldehyde

The mechanism of cycloaddition reaction between phosphenium cation and phosphindene with formaldehyde has been systematically investigated at the B3LYP/6-311++G(d,p) level of theory in order to better understand the reactivity for the valence isoelectronic of carbene. Phosphenium cation acts as an electrophilic reagent and accepts σ electrons of formaldehyde to form a complex in the first addition step. The greater the positive charge on phosphorus atom in phosphenium cation, the more stable the formed complex is. Introduction of substituents will decrease positive charge on phosphorus atom in phosphenium cation. The order of positive charge on phosphorus atom is HP+–F > HP+–OH > HP+–NH2, which is consistent with their Lewis acidities. The complex transforms to a three-membered ring product via a transition state in the second cyclization step. The product is less stable than the complex due to its tension of small ring.

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来源期刊

Main Group Chemistry 化学-化学综合

CiteScore

2.00

自引率

26.70%

发文量

审稿时长

>12 weeks

期刊介绍： Main Group Chemistry is intended to be a primary resource for all chemistry, engineering, biological, and materials researchers in both academia and in industry with an interest in the elements from the groups 1, 2, 12–18, lanthanides and actinides. The journal is committed to maintaining a high standard for its publications. This will be ensured by a rigorous peer-review process with most articles being reviewed by at least one editorial board member. Additionally, all manuscripts will be proofread and corrected by a dedicated copy editor located at the University of Kentucky.