Jonas Krieft, Beate Neumann, Georg Stammler, Norbert Werner Mitzel
{"title":"Sb/P 受挫路易斯对的查耳酮加合物中依赖氧化作用的路易斯酸度","authors":"Jonas Krieft, Beate Neumann, Georg Stammler, Norbert Werner Mitzel","doi":"10.1039/d4dt01591f","DOIUrl":null,"url":null,"abstract":"The reactions of the Frustrated Lewis Pair (F5C2)2SbCH2P(tBu)2 with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (F5C2)2SbCH2P(E)(tBu)2 (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetra¬chloro-ortho-¬benzo-quinone (o-chloranil) gave (F5C2)2Sb(CH2)(µ-E)P(tBu)2∙CatCl (CatCl = o-O2C6Cl4) with a central four-membered ring heterocycle for E = O, S, Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of o-chloranil, (F5C2)2SbCH2P(tBu)2∙2CatCl, which is also accessible by reaction of (F5C2)2SbCH2P(tBu)2 with o-chloranil. The synthesised compounds were characterised by NMR spectroscopy and X-ray structure analyses, and the structural properties were analysed in the light of the altered Lewis acidity due to the oxidation of the antimony atoms.","PeriodicalId":71,"journal":{"name":"Dalton Transactions","volume":null,"pages":null},"PeriodicalIF":3.5000,"publicationDate":"2024-06-24","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Oxidation-Dependent Lewis Acidity in Chalcogen Adducts of Sb/P Frustrated Lewis Pairs\",\"authors\":\"Jonas Krieft, Beate Neumann, Georg Stammler, Norbert Werner Mitzel\",\"doi\":\"10.1039/d4dt01591f\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"The reactions of the Frustrated Lewis Pair (F5C2)2SbCH2P(tBu)2 with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (F5C2)2SbCH2P(E)(tBu)2 (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetra¬chloro-ortho-¬benzo-quinone (o-chloranil) gave (F5C2)2Sb(CH2)(µ-E)P(tBu)2∙CatCl (CatCl = o-O2C6Cl4) with a central four-membered ring heterocycle for E = O, S, Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of o-chloranil, (F5C2)2SbCH2P(tBu)2∙2CatCl, which is also accessible by reaction of (F5C2)2SbCH2P(tBu)2 with o-chloranil. The synthesised compounds were characterised by NMR spectroscopy and X-ray structure analyses, and the structural properties were analysed in the light of the altered Lewis acidity due to the oxidation of the antimony atoms.\",\"PeriodicalId\":71,\"journal\":{\"name\":\"Dalton Transactions\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":3.5000,\"publicationDate\":\"2024-06-24\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Dalton Transactions\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://doi.org/10.1039/d4dt01591f\",\"RegionNum\":3,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q2\",\"JCRName\":\"CHEMISTRY, INORGANIC & NUCLEAR\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Dalton Transactions","FirstCategoryId":"92","ListUrlMain":"https://doi.org/10.1039/d4dt01591f","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
摘要
受挫路易斯对 (F5C2)2SbCH2P(tBu)2 与氧、硫、硒和碲的反应产生了单氧化产物 (F5C2)2SbCH2P(E)(tBu)2(E = O、S、Se、Te)。这些缩醛加合物与四氯邻苯醌(邻氯苯醌)进一步氧化,得到了 (F5C2)2Sb(CH2)(µ-E)P(tBu)2∙CatCl (CatCl = o-O2C6Cl4),其中 E = O、S、Se 时,中心为四元环杂环。在 E = Te 的情况下,消除碲元素可得到含有两个邻氯苯胺当量的氧化产物 (F5C2)2SbCH2P(tBu)2∙2CatCl,也可通过 (F5C2)2SbCH2P(tBu)2 与邻氯苯胺反应得到。通过核磁共振光谱和 X 射线结构分析对合成的化合物进行了表征,并根据锑原子氧化导致的路易斯酸度改变对其结构特性进行了分析。
Oxidation-Dependent Lewis Acidity in Chalcogen Adducts of Sb/P Frustrated Lewis Pairs
The reactions of the Frustrated Lewis Pair (F5C2)2SbCH2P(tBu)2 with oxygen, sulphur, selenium and tellurium led to the mono-oxidation products (F5C2)2SbCH2P(E)(tBu)2 (E = O, S, Se, Te). Further oxidation of these chalcogen adducts with tetra¬chloro-ortho-¬benzo-quinone (o-chloranil) gave (F5C2)2Sb(CH2)(µ-E)P(tBu)2∙CatCl (CatCl = o-O2C6Cl4) with a central four-membered ring heterocycle for E = O, S, Se. For E = Te the elimination of elemental tellurium led to an oxidation product with two equivalents of o-chloranil, (F5C2)2SbCH2P(tBu)2∙2CatCl, which is also accessible by reaction of (F5C2)2SbCH2P(tBu)2 with o-chloranil. The synthesised compounds were characterised by NMR spectroscopy and X-ray structure analyses, and the structural properties were analysed in the light of the altered Lewis acidity due to the oxidation of the antimony atoms.
期刊介绍:
Dalton Transactions is a journal for all areas of inorganic chemistry, which encompasses the organometallic, bioinorganic and materials chemistry of the elements, with applications including synthesis, catalysis, energy conversion/storage, electrical devices and medicine. Dalton Transactions welcomes high-quality, original submissions in all of these areas and more, where the advancement of knowledge in inorganic chemistry is significant.