Lin Wu, Xinning Zhang, Michael Moos, Ivo Krummenacher, Maximilian Dietz, Arumugam Jayaraman, Rüdiger Bertermann, Qing Ye, Maik Finze, Michael Wenzel, Roland Mitric, Christoph Lambert*, Holger Braunschweig* and Lei Ji*,
{"title":"1,12-bisBMes2-p-carborane Radical Anion 中簇间的全电子析出。","authors":"Lin Wu, Xinning Zhang, Michael Moos, Ivo Krummenacher, Maximilian Dietz, Arumugam Jayaraman, Rüdiger Bertermann, Qing Ye, Maik Finze, Michael Wenzel, Roland Mitric, Christoph Lambert*, Holger Braunschweig* and Lei Ji*, ","doi":"10.1021/jacs.4c03873","DOIUrl":null,"url":null,"abstract":"<p >Conjugation between three-dimensional (3D) carboranes and the attached substituents is commonly believed to be very weak. In this paper, we report that reducing 1,12-bis(BMes<sub>2</sub>)-<i>p</i>-carborane (<b>B</b><sub><b>2</b></sub><i><b>p</b></i><b>Cab</b>) with one electron gives a radical anion with a centrosymmetric semiquinoidal structure. This radical anion shows extensive electron delocalization between the two boron centers over the <i>p</i>-carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes<sub>2</sub> LUMO. Unlike dianions of other C<sub>2</sub>B<sub>10</sub>H<sub>12</sub> carboranes, which rearrange to a <i>nido</i>-form, two-electron reduction of <b>B</b><sub><b>2</b></sub><i><b>p</b></i><b>Cab</b> leads to a rearrangement into a basket-shaped intermediate.</p>","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-06-08","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Full Electron Delocalization across the Cluster in 1,12-bisBMes2-p-carborane Radical Anion\",\"authors\":\"Lin Wu, Xinning Zhang, Michael Moos, Ivo Krummenacher, Maximilian Dietz, Arumugam Jayaraman, Rüdiger Bertermann, Qing Ye, Maik Finze, Michael Wenzel, Roland Mitric, Christoph Lambert*, Holger Braunschweig* and Lei Ji*, \",\"doi\":\"10.1021/jacs.4c03873\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >Conjugation between three-dimensional (3D) carboranes and the attached substituents is commonly believed to be very weak. In this paper, we report that reducing 1,12-bis(BMes<sub>2</sub>)-<i>p</i>-carborane (<b>B</b><sub><b>2</b></sub><i><b>p</b></i><b>Cab</b>) with one electron gives a radical anion with a centrosymmetric semiquinoidal structure. This radical anion shows extensive electron delocalization between the two boron centers over the <i>p</i>-carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes<sub>2</sub> LUMO. Unlike dianions of other C<sub>2</sub>B<sub>10</sub>H<sub>12</sub> carboranes, which rearrange to a <i>nido</i>-form, two-electron reduction of <b>B</b><sub><b>2</b></sub><i><b>p</b></i><b>Cab</b> leads to a rearrangement into a basket-shaped intermediate.</p>\",\"PeriodicalId\":49,\"journal\":{\"name\":\"Journal of the American Chemical Society\",\"volume\":null,\"pages\":null},\"PeriodicalIF\":14.4000,\"publicationDate\":\"2024-06-08\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Journal of the American Chemical Society\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/jacs.4c03873\",\"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":"Journal of the American Chemical Society","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/jacs.4c03873","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
Full Electron Delocalization across the Cluster in 1,12-bisBMes2-p-carborane Radical Anion
Conjugation between three-dimensional (3D) carboranes and the attached substituents is commonly believed to be very weak. In this paper, we report that reducing 1,12-bis(BMes2)-p-carborane (B2pCab) with one electron gives a radical anion with a centrosymmetric semiquinoidal structure. This radical anion shows extensive electron delocalization between the two boron centers over the p-carborane bridge due to the overlap of carborane lowest unoccupied molecular orbital (LUMO) and the BMes2 LUMO. Unlike dianions of other C2B10H12 carboranes, which rearrange to a nido-form, two-electron reduction of B2pCab leads to a rearrangement into a basket-shaped intermediate.
期刊介绍:
The flagship journal of the American Chemical Society, known as the Journal of the American Chemical Society (JACS), has been a prestigious publication since its establishment in 1879. It holds a preeminent position in the field of chemistry and related interdisciplinary sciences. JACS is committed to disseminating cutting-edge research papers, covering a wide range of topics, and encompasses approximately 19,000 pages of Articles, Communications, and Perspectives annually. With a weekly publication frequency, JACS plays a vital role in advancing the field of chemistry by providing essential research.