Miray Aklan, Jonathan Kieselbach, Christopher Golz and Malte Fischer*,
{"title":"二芳基取代锡炔的动力学稳定：N2O反应活性、分子内C-H活化和晶体（末端）Li(THF)2作为锡化学中的通用前驱体","authors":"Miray Aklan, Jonathan Kieselbach, Christopher Golz and Malte Fischer*, ","doi":"10.1021/acs.organomet.5c00203","DOIUrl":null,"url":null,"abstract":"<p >The reactivity of the kinetically stabilized stannylene (<sup>Mes</sup>Ter)<sub>2</sub>Sn (<b>1</b>) (<sup>Mes</sup>Ter = –C<sub>6</sub>H<sub>3</sub>-2,6-(2,4,6-Me<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>) toward N<sub>2</sub>O is revisited, yielding the terminal tin(IV) hydroxide <b>2</b> via formal intramolecular C(sp<sup>3</sup>)–H activation of a putative terminal stannanone intermediate. By switching to Eind ligation (Eind = 1,1,3,3,5,5,7,7-octaethyl-<i>s</i>-hydrindacen-4-yl) at the tin center, the synthesis and characterization of the crystalline lithium salt (Eind)Li(THF)<sub>2</sub> (<b>3</b>) is reported, serving as a straightforward precursor for the clean generation of the corresponding stannylene (Eind)<sub>2</sub>Sn (<b>4</b>). Compound <b>4</b> can be further cleanly converted into the heteroleptic Eind/halide stannylene (Eind)SnCl (<b>6</b>). Both <b>4</b> and <b>6</b> serve as suitable precursors for the synthesis of the heteroleptic <i>s</i>-hydrindacene-/amido-substituted stannylene (Eind)Sn{N(SiMe<sub>3</sub>)<sub>2</sub>} (<b>5</b>).</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 15","pages":"1705–1712"},"PeriodicalIF":2.9000,"publicationDate":"2025-07-21","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00203","citationCount":"0","resultStr":"{\"title\":\"Kinetic Stabilization in Diaryl-Substituted Stannylenes: N2O Reactivity, Intramolecular C–H Activation, and Crystalline (Eind)Li(THF)2 as a Versatile Precursor in Tin Chemistry\",\"authors\":\"Miray Aklan, Jonathan Kieselbach, Christopher Golz and Malte Fischer*, \",\"doi\":\"10.1021/acs.organomet.5c00203\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >The reactivity of the kinetically stabilized stannylene (<sup>Mes</sup>Ter)<sub>2</sub>Sn (<b>1</b>) (<sup>Mes</sup>Ter = –C<sub>6</sub>H<sub>3</sub>-2,6-(2,4,6-Me<sub>3</sub>-C<sub>6</sub>H<sub>2</sub>)<sub>2</sub>) toward N<sub>2</sub>O is revisited, yielding the terminal tin(IV) hydroxide <b>2</b> via formal intramolecular C(sp<sup>3</sup>)–H activation of a putative terminal stannanone intermediate. By switching to Eind ligation (Eind = 1,1,3,3,5,5,7,7-octaethyl-<i>s</i>-hydrindacen-4-yl) at the tin center, the synthesis and characterization of the crystalline lithium salt (Eind)Li(THF)<sub>2</sub> (<b>3</b>) is reported, serving as a straightforward precursor for the clean generation of the corresponding stannylene (Eind)<sub>2</sub>Sn (<b>4</b>). Compound <b>4</b> can be further cleanly converted into the heteroleptic Eind/halide stannylene (Eind)SnCl (<b>6</b>). Both <b>4</b> and <b>6</b> serve as suitable precursors for the synthesis of the heteroleptic <i>s</i>-hydrindacene-/amido-substituted stannylene (Eind)Sn{N(SiMe<sub>3</sub>)<sub>2</sub>} (<b>5</b>).</p>\",\"PeriodicalId\":56,\"journal\":{\"name\":\"Organometallics\",\"volume\":\"44 15\",\"pages\":\"1705–1712\"},\"PeriodicalIF\":2.9000,\"publicationDate\":\"2025-07-21\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/pdf/10.1021/acs.organomet.5c00203\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"Organometallics\",\"FirstCategoryId\":\"92\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.organomet.5c00203\",\"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.5c00203","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
Kinetic Stabilization in Diaryl-Substituted Stannylenes: N2O Reactivity, Intramolecular C–H Activation, and Crystalline (Eind)Li(THF)2 as a Versatile Precursor in Tin Chemistry
The reactivity of the kinetically stabilized stannylene (MesTer)2Sn (1) (MesTer = –C6H3-2,6-(2,4,6-Me3-C6H2)2) toward N2O is revisited, yielding the terminal tin(IV) hydroxide 2 via formal intramolecular C(sp3)–H activation of a putative terminal stannanone intermediate. By switching to Eind ligation (Eind = 1,1,3,3,5,5,7,7-octaethyl-s-hydrindacen-4-yl) at the tin center, the synthesis and characterization of the crystalline lithium salt (Eind)Li(THF)2 (3) is reported, serving as a straightforward precursor for the clean generation of the corresponding stannylene (Eind)2Sn (4). Compound 4 can be further cleanly converted into the heteroleptic Eind/halide stannylene (Eind)SnCl (6). Both 4 and 6 serve as suitable precursors for the synthesis of the heteroleptic s-hydrindacene-/amido-substituted stannylene (Eind)Sn{N(SiMe3)2} (5).
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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