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
{"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":"10 1","pages":""},"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\":\"10 1\",\"pages\":\"\"},\"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}
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。
查看原文
分享 分享
微信好友 朋友圈 QQ好友 复制链接
本刊更多论文
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.
求助全文
通过发布文献求助,成功后即可免费获取论文全文。 去求助
来源期刊
Main Group Chemistry
Main Group Chemistry 化学-化学综合
CiteScore
2.00
自引率
26.70%
发文量
65
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.
期刊最新文献
Sulfone-infused covalent organic polymer derived from poly(2-aminothiophenol) and erythrosine B as an excellent tool for C–H activation Synthesis and single crystal X-ray studies of bis-(trimethylsilylmethyl) tellurium diiodide through an insertion route One-pot polycondensation and characterization of melamine-based polymer for mercury and sodium hypochlorite sensing In silico antibacterial, anticancer, antioxidant, antidiabetic activity predictions of the dual organic peroxide 2,5-dimethyl-2,5-di(tert-butyl peroxyl)hexane Syntheses characterization, and photocatalytic property of an organic-inorganic compound obtained by bromine salt and the β-Mo8O26 anion
×
引用
GB/T 7714-2015
复制
MLA
复制
APA
复制
导出至
BibTeX EndNote RefMan NoteFirst NoteExpress
×
×
提示
您的信息不完整,为了账户安全,请先补充。
现在去补充
×
提示
您因"违规操作"
具体请查看互助需知
我知道了
×
提示
现在去查看 取消
×
提示
确定
0
微信
客服QQ
Book学术公众号 扫码关注我们
反馈
×
意见反馈
请填写您的意见或建议
请填写您的手机或邮箱
已复制链接
已复制链接
快去分享给好友吧!
我知道了
×
扫码分享
扫码分享
Book学术官方微信
Book学术文献互助
Book学术文献互助群
群 号:481959085
Book学术
文献互助 智能选刊 最新文献 互助须知 联系我们:info@booksci.cn
Book学术提供免费学术资源搜索服务,方便国内外学者检索中英文文献。致力于提供最便捷和优质的服务体验。
Copyright © 2023 Book学术 All rights reserved.
ghs 京公网安备 11010802042870号 京ICP备2023020795号-1