{"title":"含大环基团的有机锑(I)化合物：二苯胺和环四替巴胺的选择性合成和表征","authors":"Yuria Kawase, , , Kei Ota, , , Shotaro Ikoma, , , Kiyoto Sugahara, , , Tsukasa Nakahodo, , , Yoshiyuki Mizuhata, , and , Tsukasa Matsuo*, ","doi":"10.1021/acs.organomet.5c00264","DOIUrl":null,"url":null,"abstract":"<p >The bulky Rind-substituted dihalostibanes, (Rind)SbX<sub>2</sub> (<b>1-X</b><sub><b>2</b></sub>) [X = Cl and Br; Rind = Eind (<b>a</b>: R<sup>1</sup> = R<sup>2</sup> = Et) and EMind (<b>b</b>: R<sup>1</sup> = Et, R<sup>2</sup> = Me)], were prepared by the reaction of SbCl<sub>3</sub> with a mixture of (Rind)Li and LiBr in THF (Rind = 1,1,7,7-tetra-R<sup>1</sup>-3,3,5,5-tetra-R<sup>2</sup>-<i>s</i>-hydrindacen-4-yl). The reduction of <b>1-X</b><sub><b>2</b></sub> with lithium naphthalenide (LiNaph) or Li metal was carried out to access organoantimony(I) compounds. The treatment of the bulky Eind-based dihalostibane, (Eind)SbX<sub>2</sub> (<b>1a-X</b><sub><b>2</b></sub>), with LiNaph in THF afforded a distibene, (Eind)Sb═Sb(Eind) (<b>2a</b>), featuring an Sb═Sb double bond. In contrast, the less bulky EMind-based dihalostibane, (EMind)SbX<sub>2</sub> (<b>1b-X</b><sub><b>2</b></sub>), reacted with Li metal in THF to yield a four-membered ring compound, cyclotetrastibane, Sb<sub>4</sub>(EMind)<sub>4</sub> (<b>3b</b>). The molecular structures and electronic properties of the resulting Sb(I) species were investigated both experimentally and theoretically.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 19","pages":"2240–2249"},"PeriodicalIF":2.9000,"publicationDate":"2025-09-13","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":"{\"title\":\"Organoantimony(I) Compounds Incorporating the Bulky Rind Groups: Selective Synthesis and Characterization of Distibene and Cyclotetrastibane\",\"authors\":\"Yuria Kawase, , , Kei Ota, , , Shotaro Ikoma, , , Kiyoto Sugahara, , , Tsukasa Nakahodo, , , Yoshiyuki Mizuhata, , and , Tsukasa Matsuo*, \",\"doi\":\"10.1021/acs.organomet.5c00264\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The bulky Rind-substituted dihalostibanes, (Rind)SbX<sub>2</sub> (<b>1-X</b><sub><b>2</b></sub>) [X = Cl and Br; Rind = Eind (<b>a</b>: R<sup>1</sup> = R<sup>2</sup> = Et) and EMind (<b>b</b>: R<sup>1</sup> = Et, R<sup>2</sup> = Me)], were prepared by the reaction of SbCl<sub>3</sub> with a mixture of (Rind)Li and LiBr in THF (Rind = 1,1,7,7-tetra-R<sup>1</sup>-3,3,5,5-tetra-R<sup>2</sup>-<i>s</i>-hydrindacen-4-yl). The reduction of <b>1-X</b><sub><b>2</b></sub> with lithium naphthalenide (LiNaph) or Li metal was carried out to access organoantimony(I) compounds. The treatment of the bulky Eind-based dihalostibane, (Eind)SbX<sub>2</sub> (<b>1a-X</b><sub><b>2</b></sub>), with LiNaph in THF afforded a distibene, (Eind)Sb═Sb(Eind) (<b>2a</b>), featuring an Sb═Sb double bond. In contrast, the less bulky EMind-based dihalostibane, (EMind)SbX<sub>2</sub> (<b>1b-X</b><sub><b>2</b></sub>), reacted with Li metal in THF to yield a four-membered ring compound, cyclotetrastibane, Sb<sub>4</sub>(EMind)<sub>4</sub> (<b>3b</b>). The molecular structures and electronic properties of the resulting Sb(I) species were investigated both experimentally and theoretically.</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"44 19\",\"pages\":\"2240–2249\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-09-13\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.5c00264\",\"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":"Organometallics","FirstCategoryId":"92","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.organomet.5c00264","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Organoantimony(I) Compounds Incorporating the Bulky Rind Groups: Selective Synthesis and Characterization of Distibene and Cyclotetrastibane
The bulky Rind-substituted dihalostibanes, (Rind)SbX2 (1-X2) [X = Cl and Br; Rind = Eind (a: R1 = R2 = Et) and EMind (b: R1 = Et, R2 = Me)], were prepared by the reaction of SbCl3 with a mixture of (Rind)Li and LiBr in THF (Rind = 1,1,7,7-tetra-R1-3,3,5,5-tetra-R2-s-hydrindacen-4-yl). The reduction of 1-X2 with lithium naphthalenide (LiNaph) or Li metal was carried out to access organoantimony(I) compounds. The treatment of the bulky Eind-based dihalostibane, (Eind)SbX2 (1a-X2), with LiNaph in THF afforded a distibene, (Eind)Sb═Sb(Eind) (2a), featuring an Sb═Sb double bond. In contrast, the less bulky EMind-based dihalostibane, (EMind)SbX2 (1b-X2), reacted with Li metal in THF to yield a four-membered ring compound, cyclotetrastibane, Sb4(EMind)4 (3b). The molecular structures and electronic properties of the resulting Sb(I) species were investigated both experimentally and theoretically.
期刊介绍：
Organometallics is the flagship journal of organometallic chemistry and records progress in one of the most active fields of science, bridging organic and inorganic chemistry. The journal publishes Articles, Communications, Reviews, and Tutorials (instructional overviews) that depict research on the synthesis, structure, bonding, chemical reactivity, and reaction mechanisms for a variety of applications, including catalyst design and catalytic processes; main-group, transition-metal, and lanthanide and actinide metal chemistry; synthetic aspects of polymer science and materials science; and bioorganometallic chemistry.
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