{"title":"磷酸阳离子与甲醛环加成反应的理论研究","authors":"Jiandong Sun, Xiaojun Tan, Huilian Xu, Xiujun Zhang, Yan He, Jinsong Gu","doi":"10.3233/mgc-220037","DOIUrl":null,"url":null,"abstract":"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.","PeriodicalId":18027,"journal":{"name":"Main Group Chemistry","volume":null,"pages":null},"PeriodicalIF":1.3000,"publicationDate":"2022-04-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Theoretical study on the cycloaddition reaction of phosphenium cation and formaldehyde\",\"authors\":\"Jiandong Sun, Xiaojun Tan, Huilian Xu, Xiujun Zhang, Yan He, Jinsong Gu\",\"doi\":\"10.3233/mgc-220037\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"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.\",\"PeriodicalId\":18027,\"journal\":{\"name\":\"Main Group Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.3000,\"publicationDate\":\"2022-04-16\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Main Group Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.3233/mgc-220037\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Main Group Chemistry","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.3233/mgc-220037","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
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.
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.