{"title":"一组不寻常开环电环反应的环选择性研究:通过自然键轨道分析和分子中原子的量子理论确定电子键结构,并通过键反应性描述符分析电子反应机理","authors":"Jesús Sánchez-Márquez, Alejandro Morales-Bayuelo","doi":"10.1002/qua.27494","DOIUrl":null,"url":null,"abstract":"<div>\n \n <p>In this work, we have studied the torquoselectivity of a set of unusual ring-opening electrocyclic reactions that have not been successfully rationalized using models based on orbital symmetry nor have they been explained by steric hindrance. Firstly, the corresponding transition states have been obtained, and it has been verified that the intrinsic reaction coordinates associated with these transition states are consistent with the reactants and products of the reactions studied. This has allowed us to theoretically calculate the reaction barriers (with their corresponding thermal corrections) and compare them with the corresponding experimental values. In a second step, we have analyzed the electronic bonding structure using the methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, searching for interactions that may significantly stabilize the transition states. Finally, we have analyzed the reactivity using a recent model that has allowed us to calculate the corresponding bond reactivity descriptors.</p>\n </div>","PeriodicalId":182,"journal":{"name":"International Journal of Quantum Chemistry","volume":null,"pages":null},"PeriodicalIF":2.3000,"publicationDate":"2024-10-07","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Study of the Torquoselectivity of a Set of Unusual Ring-Opening Electrocyclic Reactions: Determination of the Electronic Bonding Structure Through the Methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, and Analysis of the Electronic Reaction Mechanism Through Bond Reactivity Descriptors\",\"authors\":\"Jesús Sánchez-Márquez, Alejandro Morales-Bayuelo\",\"doi\":\"10.1002/qua.27494\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div>\\n \\n <p>In this work, we have studied the torquoselectivity of a set of unusual ring-opening electrocyclic reactions that have not been successfully rationalized using models based on orbital symmetry nor have they been explained by steric hindrance. Firstly, the corresponding transition states have been obtained, and it has been verified that the intrinsic reaction coordinates associated with these transition states are consistent with the reactants and products of the reactions studied. This has allowed us to theoretically calculate the reaction barriers (with their corresponding thermal corrections) and compare them with the corresponding experimental values. In a second step, we have analyzed the electronic bonding structure using the methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, searching for interactions that may significantly stabilize the transition states. Finally, we have analyzed the reactivity using a recent model that has allowed us to calculate the corresponding bond reactivity descriptors.</p>\\n </div>\",\"PeriodicalId\":182,\"journal\":{\"name\":\"International Journal of Quantum Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.3000,\"publicationDate\":\"2024-10-07\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"International Journal of Quantum Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/qua.27494\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"International Journal of Quantum Chemistry","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/qua.27494","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
Study of the Torquoselectivity of a Set of Unusual Ring-Opening Electrocyclic Reactions: Determination of the Electronic Bonding Structure Through the Methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, and Analysis of the Electronic Reaction Mechanism Through Bond Reactivity Descriptors
In this work, we have studied the torquoselectivity of a set of unusual ring-opening electrocyclic reactions that have not been successfully rationalized using models based on orbital symmetry nor have they been explained by steric hindrance. Firstly, the corresponding transition states have been obtained, and it has been verified that the intrinsic reaction coordinates associated with these transition states are consistent with the reactants and products of the reactions studied. This has allowed us to theoretically calculate the reaction barriers (with their corresponding thermal corrections) and compare them with the corresponding experimental values. In a second step, we have analyzed the electronic bonding structure using the methodologies of Natural Bond Orbital Analysis and Quantum Theory of Atoms in Molecules, searching for interactions that may significantly stabilize the transition states. Finally, we have analyzed the reactivity using a recent model that has allowed us to calculate the corresponding bond reactivity descriptors.
期刊介绍:
Since its first formulation quantum chemistry has provided the conceptual and terminological framework necessary to understand atoms, molecules and the condensed matter. Over the past decades synergistic advances in the methodological developments, software and hardware have transformed quantum chemistry in a truly interdisciplinary science that has expanded beyond its traditional core of molecular sciences to fields as diverse as chemistry and catalysis, biophysics, nanotechnology and material science.