{"title":"A Lead(II) Substituted Triplet Carbene","authors":"Fabian Dankert, Julian Messelberger, Ugo Authesserre, Abinash Swain, David Scheschkewitz, Bernd Morgenstern, Dominik Munz","doi":"10.1021/jacs.4c10205","DOIUrl":null,"url":null,"abstract":"Reaction of the pincer-type ligand L<sub>3</sub> supported complex [L<sub>3</sub>PbBr][BArF<sub>24</sub>] (<b>1</b>) with Li[(C(═N<sub>2</sub>)TMS)] furnishes [L<sub>3</sub>Pb(C(═N<sub>2</sub>)TMS)][BArF<sub>24</sub>] (<b>2</b>). Diazo-compound <b>2</b> eliminates dinitrogen upon irradiation affording formal plumba-alkyne <b>3</b>, which persists in cold fluoroarene solutions. Variable temperature UV/Vis and NMR spectroscopies in combination with quantum-chemical calculations identify <b>3</b> as a metal-substituted triplet carbene. In-crystallo irradiation of [L<sub>3</sub>Pb(C(═N<sub>2</sub>)TMS)(tol)][BArF<sub>24</sub>] (<b>2</b>·tol) provides a snapshot of intermolecular C–H bond insertion with toluene (<b>4</b>).","PeriodicalId":49,"journal":{"name":"Journal of the American Chemical Society","volume":null,"pages":null},"PeriodicalIF":14.4000,"publicationDate":"2024-10-18","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://doi.org/10.1021/jacs.4c10205","RegionNum":1,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q1","JCRName":"CHEMISTRY, MULTIDISCIPLINARY","Score":null,"Total":0}
引用次数: 0
Abstract
Reaction of the pincer-type ligand L3 supported complex [L3PbBr][BArF24] (1) with Li[(C(═N2)TMS)] furnishes [L3Pb(C(═N2)TMS)][BArF24] (2). Diazo-compound 2 eliminates dinitrogen upon irradiation affording formal plumba-alkyne 3, which persists in cold fluoroarene solutions. Variable temperature UV/Vis and NMR spectroscopies in combination with quantum-chemical calculations identify 3 as a metal-substituted triplet carbene. In-crystallo irradiation of [L3Pb(C(═N2)TMS)(tol)][BArF24] (2·tol) provides a snapshot of intermolecular C–H bond insertion with toluene (4).
期刊介绍:
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