Breaking and Entering: Diazene Cleavage and Insertion into U(III)–Si Bonds

IF 2.5 3区化学 Q2 CHEMISTRY, INORGANIC & NUCLEAR

Organometallics Pub Date : 2024-12-20 DOI:10.1021/acs.organomet.4c0044910.1021/acs.organomet.4c00449

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":"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.","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.

Abstract Image

查看原文本刊更多论文

求助全文

约1分钟内获得全文求助全文

来源期刊

Organometallics 化学-无机化学与核化学

CiteScore

5.60

自引率

7.10%

发文量

382

审稿时长

1.7 months

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.