{"title":"关于 COCl 2 和 OCY 分子(Y = S、Se 和 Te)相互作用产生的σ孔和π孔对配合物稳定性的竞争的理论研究","authors":"","doi":"10.1080/10426507.2024.2378049","DOIUrl":null,"url":null,"abstract":"<div><div>Carbonyl dichloride (COCl<sub>2</sub>), also known as phosgene, is a highly toxic gas, whose exposure or acute inhalation causes severe respiratory complications, such as pulmonary edema, pulmonary emphysema, and even death. In this study, we theoretically investigated the complexes formed by the interaction between the COCl<sub>2</sub> (phosgene) and OCY molecules (Y = S, Se, and Te). Complex geometry optimization yielded three distinct types of conformations. Conformation-I complexes were stabilized by two concurring chalcogen-bonding interactions (i.e. O⋯Y and Cl⋯Y) by forming a ring structure. However, only a single linear interaction (O⋯C) or (O⋯Cl) occurred in conformation-II and III complexes, forming complexes with the nature of tetrel and halogen bonds, respectively. According to the results of the molecular electrostatic potential (MEP), interaction energy (ΔE<sup>T</sup>), natural bond orbital (NBO), and so on, the σ-hole of the Y atom in the OCY molecule exhibited higher acidic strength and formed more stable complexes than those resulting from the σ- and π-holes of the COCl<sub>2</sub> molecule.</div></div>","PeriodicalId":20056,"journal":{"name":"Phosphorus, Sulfur, and Silicon and the Related Elements","volume":null,"pages":null},"PeriodicalIF":1.4000,"publicationDate":"2024-06-02","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"A theoretical investigation of the competition between σ- and π-holes on the stability of the complexes resulting from the interaction between the COCl2 and OCY molecules (Y = S, Se, and Te)\",\"authors\":\"\",\"doi\":\"10.1080/10426507.2024.2378049\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><div>Carbonyl dichloride (COCl<sub>2</sub>), also known as phosgene, is a highly toxic gas, whose exposure or acute inhalation causes severe respiratory complications, such as pulmonary edema, pulmonary emphysema, and even death. In this study, we theoretically investigated the complexes formed by the interaction between the COCl<sub>2</sub> (phosgene) and OCY molecules (Y = S, Se, and Te). Complex geometry optimization yielded three distinct types of conformations. Conformation-I complexes were stabilized by two concurring chalcogen-bonding interactions (i.e. O⋯Y and Cl⋯Y) by forming a ring structure. However, only a single linear interaction (O⋯C) or (O⋯Cl) occurred in conformation-II and III complexes, forming complexes with the nature of tetrel and halogen bonds, respectively. According to the results of the molecular electrostatic potential (MEP), interaction energy (ΔE<sup>T</sup>), natural bond orbital (NBO), and so on, the σ-hole of the Y atom in the OCY molecule exhibited higher acidic strength and formed more stable complexes than those resulting from the σ- and π-holes of the COCl<sub>2</sub> molecule.</div></div>\",\"PeriodicalId\":20056,\"journal\":{\"name\":\"Phosphorus, Sulfur, and Silicon and the Related Elements\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":1.4000,\"publicationDate\":\"2024-06-02\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Phosphorus, Sulfur, and Silicon and the Related Elements\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1042650724000297\",\"RegionNum\":4,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q4\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Phosphorus, Sulfur, and Silicon and the Related Elements","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1042650724000297","RegionNum":4,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q4","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
二氯化碳(COCl2)又称光气,是一种剧毒气体,接触或急性吸入会引起严重的呼吸道并发症,如肺水肿、肺气肿,甚至死亡。在这项研究中,我们从理论上研究了 COCl2(光气)和 OCY 分子(Y = S、Se 和 Te)相互作用形成的复合物。通过优化配合物的几何结构,我们得出了三种不同的构象。构象-I 复合物通过形成环状结构,由两个并存的查尔根键相互作用(即 O⋯Y 和 Cl⋯Y)稳定下来。然而,在构象 II 和构象 III 复合物中只出现了单一的线性相互作用(O⋯C)或(O⋯Cl),分别形成了具有四键和卤素键性质的复合物。根据分子静电势(MEP)、相互作用能(ΔET)、天然键轨道(NBO)等结果,OCY 分子中 Y 原子的σ孔比 COCl2 分子的σ孔和π孔具有更高的酸性,形成的络合物也更稳定。
A theoretical investigation of the competition between σ- and π-holes on the stability of the complexes resulting from the interaction between the COCl2 and OCY molecules (Y = S, Se, and Te)
Carbonyl dichloride (COCl2), also known as phosgene, is a highly toxic gas, whose exposure or acute inhalation causes severe respiratory complications, such as pulmonary edema, pulmonary emphysema, and even death. In this study, we theoretically investigated the complexes formed by the interaction between the COCl2 (phosgene) and OCY molecules (Y = S, Se, and Te). Complex geometry optimization yielded three distinct types of conformations. Conformation-I complexes were stabilized by two concurring chalcogen-bonding interactions (i.e. O⋯Y and Cl⋯Y) by forming a ring structure. However, only a single linear interaction (O⋯C) or (O⋯Cl) occurred in conformation-II and III complexes, forming complexes with the nature of tetrel and halogen bonds, respectively. According to the results of the molecular electrostatic potential (MEP), interaction energy (ΔET), natural bond orbital (NBO), and so on, the σ-hole of the Y atom in the OCY molecule exhibited higher acidic strength and formed more stable complexes than those resulting from the σ- and π-holes of the COCl2 molecule.
期刊介绍:
Phosphorus, Sulfur, and Silicon and the Related Elements is a monthly publication intended to disseminate current trends and novel methods to those working in the broad and interdisciplinary field of heteroatom chemistry.