{"title":"多硒化物和多硫化物的性质和反应性的量子化学研究","authors":"Hui-Chu Pi , Ching-Han Hu","doi":"10.1080/17415993.2022.2152284","DOIUrl":null,"url":null,"abstract":"<div><p>High-level ab initio and density functional theory were applied to investigate property and reactivity of polyselenides and polysulfides. With CH<sub>3</sub>X<sub>n</sub>H (X = S or Se) we found that the deprotonation energy (and p<em>K<sub>a</sub></em>) of CH<sub>3</sub>Se<sub>n</sub>H, ionization potential (IP) of, and CH<sub>3</sub>Se<sub>n</sub>−H bond dissociation energy (BDE) are lower than those of their sulfur counterparts. For <em>n</em> = 2, IPs and X−H BDEs are exceptionally small. The relative nucleophilicity of <span><math><mrow><mtext>C</mtext></mrow><mrow><msub><mrow><mtext>H</mtext></mrow><mn>3</mn></msub></mrow><msubsup><mrow><mtext>X</mtext></mrow><mi>n</mi><mo>−</mo></msubsup></math></span> vary with substrates. However, CH<sub>3</sub>Se<sub>n</sub>H are more nucleophilic than CH<sub>3</sub>S<sub>n</sub>H due to their due to their lower deprotonation energy. The nucleophilicity of selenolates versus thiolates are related to the chemical nature. Selenium is more electrophilic than sulfur.</p></div>","PeriodicalId":17081,"journal":{"name":"Journal of Sulfur Chemistry","volume":null,"pages":null},"PeriodicalIF":2.1000,"publicationDate":"2023-06-01","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Property and reactivity of polyselenides and polysulfides: a quantum chemistry study\",\"authors\":\"Hui-Chu Pi , Ching-Han Hu\",\"doi\":\"10.1080/17415993.2022.2152284\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<div><p>High-level ab initio and density functional theory were applied to investigate property and reactivity of polyselenides and polysulfides. With CH<sub>3</sub>X<sub>n</sub>H (X = S or Se) we found that the deprotonation energy (and p<em>K<sub>a</sub></em>) of CH<sub>3</sub>Se<sub>n</sub>H, ionization potential (IP) of, and CH<sub>3</sub>Se<sub>n</sub>−H bond dissociation energy (BDE) are lower than those of their sulfur counterparts. For <em>n</em> = 2, IPs and X−H BDEs are exceptionally small. The relative nucleophilicity of <span><math><mrow><mtext>C</mtext></mrow><mrow><msub><mrow><mtext>H</mtext></mrow><mn>3</mn></msub></mrow><msubsup><mrow><mtext>X</mtext></mrow><mi>n</mi><mo>−</mo></msubsup></math></span> vary with substrates. However, CH<sub>3</sub>Se<sub>n</sub>H are more nucleophilic than CH<sub>3</sub>S<sub>n</sub>H due to their due to their lower deprotonation energy. The nucleophilicity of selenolates versus thiolates are related to the chemical nature. Selenium is more electrophilic than sulfur.</p></div>\",\"PeriodicalId\":17081,\"journal\":{\"name\":\"Journal of Sulfur Chemistry\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":2.1000,\"publicationDate\":\"2023-06-01\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of Sulfur Chemistry\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://www.sciencedirect.com/org/science/article/pii/S1741599323000065\",\"RegionNum\":3,\"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":"Journal of Sulfur Chemistry","FirstCategoryId":"92","ListUrlMain":"https://www.sciencedirect.com/org/science/article/pii/S1741599323000065","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Property and reactivity of polyselenides and polysulfides: a quantum chemistry study
High-level ab initio and density functional theory were applied to investigate property and reactivity of polyselenides and polysulfides. With CH3XnH (X = S or Se) we found that the deprotonation energy (and pKa) of CH3SenH, ionization potential (IP) of, and CH3Sen−H bond dissociation energy (BDE) are lower than those of their sulfur counterparts. For n = 2, IPs and X−H BDEs are exceptionally small. The relative nucleophilicity of vary with substrates. However, CH3SenH are more nucleophilic than CH3SnH due to their due to their lower deprotonation energy. The nucleophilicity of selenolates versus thiolates are related to the chemical nature. Selenium is more electrophilic than sulfur.
期刊介绍:
The Journal of Sulfur Chemistry is an international journal for the dissemination of scientific results in the rapidly expanding realm of sulfur chemistry. The journal publishes high quality reviews, full papers and communications in the following areas: organic and inorganic chemistry, industrial chemistry, materials and polymer chemistry, biological chemistry and interdisciplinary studies directly related to sulfur science.
Papers outlining theoretical, physical, mechanistic or synthetic studies pertaining to sulfur chemistry are welcome. Hence the target audience is made up of academic and industrial chemists with peripheral or focused interests in sulfur chemistry. Manuscripts that truly define the aims of the journal include, but are not limited to, those that offer: a) innovative use of sulfur reagents; b) new synthetic approaches to sulfur-containing biomolecules, materials or organic and organometallic compounds; c) theoretical and physical studies that facilitate the understanding of sulfur structure, bonding or reactivity; d) catalytic, selective, synthetically useful or noteworthy transformations of sulfur containing molecules; e) industrial applications of sulfur chemistry; f) unique sulfur atom or molecule involvement in interfacial phenomena; g) descriptions of solid phase or combinatorial methods involving sulfur containing substrates. Submissions pertaining to related atoms such as selenium and tellurium are also welcome. Articles offering routine heterocycle formation through established reactions of sulfur containing substrates are outside the scope of the journal.