Nathan J. Lin, Kelly L. Gullett, Ushindi K. Muna, Ryan Galloway, Matthias Zeller and Suzanne C. Bart*,
{"title":"Breaking and Entering: Diazene Cleavage and Insertion into U(III)–Si Bonds","authors":"Nathan J. Lin, Kelly L. Gullett, Ushindi K. Muna, Ryan Galloway, Matthias Zeller and Suzanne C. Bart*, ","doi":"10.1021/acs.organomet.4c0044910.1021/acs.organomet.4c00449","DOIUrl":null,"url":null,"abstract":"<p >Treatment of trivalent [K(18-crown-6)][U(I)<sub>2</sub>{(Si(SiMe<sub>3</sub>)<sub>2</sub>SiMe<sub>2</sub>)<sub>2</sub>O}] (<b>1-crown</b>) with aryl diazenes generated a series of uranium(IV) species of the form [(THF)U(I)<sub>2</sub>{N(R/R′)Si(SiMe<sub>3</sub>)<sub>2</sub>SiMe<sub>2</sub>}<sub>2</sub>O] (R = R′ = Ph (<b>2-Ph</b>), 4-FC<sub>6</sub>H<sub>4</sub> (<b>2-F</b>), 4-MeC<sub>6</sub>H<sub>4</sub> (<b>2-Tol</b>), 4-OMeC<sub>6</sub>H<sub>4</sub> (<b>2-Mes</b>), and R = 4-MeC<sub>6</sub>H<sub>4</sub>, R′ = Ph (<b>2-TolPh</b>). Activation of an ortho-substituted diazene, (2,4,6-Me<sub>3</sub>C<sub>6</sub>H<sub>2</sub>N)<sub>2</sub> (MesN═NMes), forms <b>2-Mes</b>, [K(18-crown-6)][U(I)<sub>3</sub>{N(Mes)Si(SiMe<sub>3</sub>)<sub>2</sub>SiMe<sub>2</sub>}<sub>2</sub>O] (<b>2-MesKI</b>), and ([K(18-crown-6][U(I)(NMes)(N[Mes]-3,3,5,5-Me<sub>4</sub>2,2,6,6-(SiMe<sub>3</sub>)<sub>4</sub>-tetrasil-3-oxane)]) (<b>3-Mes</b>). The increased sterics of this <i>ortho</i>-substituted substrate slowed insertion, facilitating the observation of <b>3-Mes</b> by in situ NMR spectroscopy. The redox potentials of the aryl diazenes (R–N═N–R′) were studied using cyclic voltammetry to elucidate their electronic contributions toward their reactivity with <b>1-crown</b>. The reaction of <b>1-crown</b> and (<i>Z</i>)-11,12-dihydrodibenzo[<i>c</i>,<i>g</i>][1,2]diazocine is also described, forming the [(THF)U(I)<sub>2</sub>{[N(C<sub>7</sub>H<sub>6</sub>)]<sub>2</sub>Si(SiMe<sub>3</sub>)<sub>2</sub>SiMe<sub>2</sub>}<sub>2</sub>O] (<b>2-diazonine</b>) and {(THF)<sub>2</sub>U(I)<sub>2</sub>[N(C<sub>7</sub>H<sub>6</sub>)]<sub>2</sub>}<sub>2</sub> (<b>4</b>) dimers.</p>","PeriodicalId":56,"journal":{"name":"Organometallics","volume":"44 1","pages":"289–299 289–299"},"PeriodicalIF":2.5000,"publicationDate":"2024-12-20","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.4c00449","RegionNum":3,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q2","JCRName":"CHEMISTRY, INORGANIC & NUCLEAR","Score":null,"Total":0}
引用次数: 0
Abstract
Treatment of trivalent [K(18-crown-6)][U(I)2{(Si(SiMe3)2SiMe2)2O}] (1-crown) with aryl diazenes generated a series of uranium(IV) species of the form [(THF)U(I)2{N(R/R′)Si(SiMe3)2SiMe2}2O] (R = R′ = Ph (2-Ph), 4-FC6H4 (2-F), 4-MeC6H4 (2-Tol), 4-OMeC6H4 (2-Mes), and R = 4-MeC6H4, R′ = Ph (2-TolPh). Activation of an ortho-substituted diazene, (2,4,6-Me3C6H2N)2 (MesN═NMes), forms 2-Mes, [K(18-crown-6)][U(I)3{N(Mes)Si(SiMe3)2SiMe2}2O] (2-MesKI), and ([K(18-crown-6][U(I)(NMes)(N[Mes]-3,3,5,5-Me42,2,6,6-(SiMe3)4-tetrasil-3-oxane)]) (3-Mes). The increased sterics of this ortho-substituted substrate slowed insertion, facilitating the observation of 3-Mes by in situ NMR spectroscopy. The redox potentials of the aryl diazenes (R–N═N–R′) were studied using cyclic voltammetry to elucidate their electronic contributions toward their reactivity with 1-crown. The reaction of 1-crown and (Z)-11,12-dihydrodibenzo[c,g][1,2]diazocine is also described, forming the [(THF)U(I)2{[N(C7H6)]2Si(SiMe3)2SiMe2}2O] (2-diazonine) and {(THF)2U(I)2[N(C7H6)]2}2 (4) dimers.
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.
京公网安备 11010802042870号
京ICP备2023020795号-1
分享
求助内容：
应助结果提醒方式：
扫码关注我们
