Dr. Deependra Bawari, Irina Malahov, Dr. Roman Dobrovetsky
{"title":"Sb-to-P Metathesis - 结构受限阳离子 PIII 化合物的直接途径","authors":"Dr. Deependra Bawari, Irina Malahov, Dr. Roman Dobrovetsky","doi":"10.1002/anie.202419772","DOIUrl":null,"url":null,"abstract":"<p>Structurally constrained, cationic P<sup>III</sup> compound [<b>LP</b>][<b>SbCl<sub>4</sub></b>] with an <i>OCO</i> pincer-type ligand (<b>L</b>) having a central carbene donor was directly synthesized via an Sb-to-P metathesis reaction between PCl<sub>3</sub> and <b>LSb-Cl</b>. [<b>LP</b>][<b>SbCl<sub>4</sub></b>] was isolated and its reactivity with small molecules (ROH and RNH<sub>2</sub>) was studied, showing that [<b>SbCl<sub>4</sub></b>]<sup>−</sup> is not an innocent counter anion, but an active participant in these reactions. When the [<b>SbCl<sub>4</sub></b>]<sup>−</sup> was replaced with the [<b>CB<sub>11</sub>H<sub>12</sub></b>]<sup>−</sup> ([<b>Cb</b>]<sup><b>−</b></sup>) anion, the reactions were redirected to [<b>LP</b>]<sup>+</sup> cation only. The reactions with alcohols and amines led to the equilibrium between the products of the formal E−H (E=O, N) bond oxidative addition to the P-center and products of the P-center/ligand-assisted bond activation. Remarkably, [<b>LP</b>]<sup>+</sup> activated the PhO−H and PhN(H)−H bonds in a reversible, thermoneutral fashion.</p>","PeriodicalId":125,"journal":{"name":"Angewandte Chemie International Edition","volume":"64 7","pages":""},"PeriodicalIF":16.1000,"publicationDate":"2024-11-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202419772","citationCount":"0","resultStr":"{\"title\":\"Sb-to-P Metathesis: A Direct Route to Structurally Constrained, Cationic PIII Compound\",\"authors\":\"Dr. Deependra Bawari, Irina Malahov, Dr. Roman Dobrovetsky\",\"doi\":\"10.1002/anie.202419772\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p>Structurally constrained, cationic P<sup>III</sup> compound [<b>LP</b>][<b>SbCl<sub>4</sub></b>] with an <i>OCO</i> pincer-type ligand (<b>L</b>) having a central carbene donor was directly synthesized via an Sb-to-P metathesis reaction between PCl<sub>3</sub> and <b>LSb-Cl</b>. [<b>LP</b>][<b>SbCl<sub>4</sub></b>] was isolated and its reactivity with small molecules (ROH and RNH<sub>2</sub>) was studied, showing that [<b>SbCl<sub>4</sub></b>]<sup>−</sup> is not an innocent counter anion, but an active participant in these reactions. When the [<b>SbCl<sub>4</sub></b>]<sup>−</sup> was replaced with the [<b>CB<sub>11</sub>H<sub>12</sub></b>]<sup>−</sup> ([<b>Cb</b>]<sup><b>−</b></sup>) anion, the reactions were redirected to [<b>LP</b>]<sup>+</sup> cation only. The reactions with alcohols and amines led to the equilibrium between the products of the formal E−H (E=O, N) bond oxidative addition to the P-center and products of the P-center/ligand-assisted bond activation. Remarkably, [<b>LP</b>]<sup>+</sup> activated the PhO−H and PhN(H)−H bonds in a reversible, thermoneutral fashion.</p>\",\"PeriodicalId\":125,\"journal\":{\"name\":\"Angewandte Chemie International Edition\",\"volume\":\"64 7\",\"pages\":\"\"},\"PeriodicalIF\":16.1000,\"publicationDate\":\"2024-11-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://onlinelibrary.wiley.com/doi/epdf/10.1002/anie.202419772\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Angewandte Chemie International Edition\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://onlinelibrary.wiley.com/doi/10.1002/anie.202419772\",\"RegionNum\":1,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q1\",\"JCRName\":\"CHEMISTRY, MULTIDISCIPLINARY\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"Angewandte Chemie International Edition","FirstCategoryId":"92","ListUrlMain":"https://onlinelibrary.wiley.com/doi/10.1002/anie.202419772","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Sb-to-P Metathesis: A Direct Route to Structurally Constrained, Cationic PIII Compound
Structurally constrained, cationic PIII compound [LP][SbCl4] with an OCO pincer-type ligand (L) having a central carbene donor was directly synthesized via an Sb-to-P metathesis reaction between PCl3 and LSb-Cl. [LP][SbCl4] was isolated and its reactivity with small molecules (ROH and RNH2) was studied, showing that [SbCl4]− is not an innocent counter anion, but an active participant in these reactions. When the [SbCl4]− was replaced with the [CB11H12]− ([Cb]−) anion, the reactions were redirected to [LP]+ cation only. The reactions with alcohols and amines led to the equilibrium between the products of the formal E−H (E=O, N) bond oxidative addition to the P-center and products of the P-center/ligand-assisted bond activation. Remarkably, [LP]+ activated the PhO−H and PhN(H)−H bonds in a reversible, thermoneutral fashion.
期刊介绍：
Angewandte Chemie, a journal of the German Chemical Society (GDCh), maintains a leading position among scholarly journals in general chemistry with an impressive Impact Factor of 16.6 (2022 Journal Citation Reports, Clarivate, 2023). Published weekly in a reader-friendly format, it features new articles almost every day. Established in 1887, Angewandte Chemie is a prominent chemistry journal, offering a dynamic blend of Review-type articles, Highlights, Communications, and Research Articles on a weekly basis, making it unique in the field.
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