Generation of Tp*2U(N3) from a family of new uranium(III) alkyl complexes

Tatebe, Caleb J.; Johnson, Sara A.; Zeller, Mat­thias; Bart, Suzanne C.

doi:10.1016/j.jorganchem.2017.09.013

Cited by 13 publications

(11 citation statements)

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“…Analysis of THF solutions of 2- para and 2- meta at ambient temperature revealed features that are consistent with trivalent U(III) complexes , around 1250 nm (400 M –1 cm –1 ), including broad features up to 1650 nm (Figure , green). The UV–visible regions (Figure , inset) for both alkynyl dimers display characteristic absorbances similar to Tp* 2 UBn and its derivatives, which are all dark green, U(III) alkyl compounds. , This is highlighted by a broad absorption around ∼680 nm, which is responsible for the observed green color. Absorbances around ∼500–800 nm are established to be color-giving d–f transitions in U(III) systems …”

Section: Resultsmentioning

confidence: 89%

“…Given that the hydrotris(3,5-dimethylpyrazolyl)borate (Tp*) ligand enables access to low-valent uranium alkyl complexes , and their reactivity, − this ligand framework is an ideal system to study electronic communication in dinuclear molecules of the form [Tp* 2 U]-(Linker)-[UTp* 2 ]. Herein, we report the synthesis of a family of diuranium complexes bridged by either alkynyl (U(III) derivatives) or imido (U(IV) derivatives) linkers.…”

Section: Introductionmentioning

confidence: 99%

“…The UV−visible regions (Figure 2, inset) for both alkynyl dimers display characteristic absorbances similar to Tp* 2 UBn and its derivatives, which are all dark green, U(III) alkyl compounds. 27,28 This is highlighted by a broad absorption around ∼680 nm, which is responsible for the observed green color. Absorbances around ∼500−800 nm are established to be color-giving d−f transitions in U(III) systems.…”

Section: ■ Introductionmentioning

confidence: 99%

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Investigation of the Electronic Structure of Aryl-Bridged Dinuclear U(III) and U(IV) Compounds

et al. 2019

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A family of dinuclear bis(Tp*) (Tp* = hydrotris(3,5dimethylpyrazolyl)borate) uranium compounds with conjugated organic linkers was synthesized to explore possible electronic communication between uranium ions. Trivalent diuranium phenyl alkynyl compounds, Tp* 2 UCC(1,3-C 6 H 4 )CCUTp* 2 (2-meta) or Tp* 2 UCC(1,4-C 6 H 4 )-CCUTp* 2 (2-para), and tetravalent diuranium phenylimido compounds, Tp* 2 U(N-1,3-C 6 H 4 −N)UTp* 2 (3-meta) and Tp* 2 U(N-1,4-C 6 H 4 − N)UTp* 2 (3-para), were generated from trivalent Tp* 2 UCH 2 Ph. All compounds were fully characterized both spectroscopically and structurally. The electronic structures of all derivatives were interrogated using magnetic measurements, electrochemistry, and were the subject of computational analyses. All of these data combined established that little electronic communication exists between the uranium centers in these trivalent and tetravalent diuranium molecules.

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Section: Resultsmentioning

confidence: 89%

Section: Introductionmentioning

confidence: 99%

Section: ■ Introductionmentioning

confidence: 99%

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Investigation of the Electronic Structure of Aryl-Bridged Dinuclear U(III) and U(IV) Compounds

et al. 2019

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“…Ta king advantage of the free metal coordination site created as ac onsequence of using the Tp* ligand,arich and manifold chemistry for the system [UTp* 2 ]h as been established including, for example, the synthesis of highly reactive Ua lkyl complexes. [73][74][75][76][77] Reactive speciesm ight enablea ctivation of small molecules such as CO 2 or the formation of new structuralm otives even under CÀCb ondf ormation or electron transfer. [40,63,[78][79][80] However,t he focus of this report lies on the synthesis of the homologousA nTp 3 compounds of trivalent5f-elements (An = U, Np, Pu, Am, Cm) togetherw ith the results of spectroscopic, magnetic and theoretical investigations, enabling as ystematic assessment of their properties.…”

Section: Introductionmentioning

confidence: 99%

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2020

Chemistry A European J

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Thei sostructural compoundso ft he trivalent actinides uranium,neptunium, plutonium, americium,a nd curium with the hydridotris(1-pyrazolyl)borato (Tp) ligand An[h 3-HB(N 2 C 3 H 3) 3 ] 3 (AnTp 3)h ave been obtained through severals ynthetic routes. Structural, spectroscopic(absorption, infrared, laser fluorescence) andm agnetic characterisa-tion of the compounds were performed in combination with crystal field, density functional theory (DFT)a nd relativistic multiconfigurationalc alculations. The covalentb ondingi nteractions were analysed in terms of the natural bond orbital (NBO)a nd quantum theory of atomsi nm olecules (QTAIM) models.

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“…117 However, because of their lack of thermal stability, actinide alkyls, [118][119][120][121][122] especially low-valent actinides, are rare. [123][124][125][126][127][128][129][130][131][132] These complexes are of interest for their small-molecule activation, 133,134 spectroscopic and magnetic properties, 135 and as starting materials for advancing the fundamental coordination chemistry and reactivity of low valent actinides. 136 To date, the organometallic chemistry of the actinides, particularly transuranic chemistry, has been dominated by π-ligands such as cyclopentadienyl and other derivatives.…”

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confidence: 99%

Synthesis and reactivity of low-valent uranium and neptunium complexes

Myers¹

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Chapter 1 reports the synthesis and characterization of U(IV) and Np(IV) selenium bis(phenolate) complexes. The reaction of the U(IV) complex with half an equivalent of p-benzoquinone results in the formation of a U(V)--U(V) species with a bridging reduced quinone. This represents a rare example of high-valent uranium chemistry as well as a rare example of a neptunium aryloxide complex. In Chapters 2 and 3 the synthesis and characterization of a rare U(III) hydrocarbyl complex, U[[eta]4-Me2NC(H)C6H5]3, and the first structurally characterized transuranic hydrocarbyl complex, Np[[eta]4-Me2NC(H)C6H5]3, complex, has been generated with four equivalents of the K[Me2NC(H)C6H5] ligand. In the analogous Th(IV) reaction, C-H bond activation of a methyl group of one dimethylamine was observed yielding Th[[eta]4-Me2NC(H)C6H5]2[[eta]5-(CH2)MeNC(H)C6H5] with a dianionic DMBA ligand. The utility of these complexes as starting materials has been analyzed using a bulky dithiocarboxylate ligand to yield tetravalent actinide species for U and Th but Np maintains the trivalent oxidation state. Chapter 4 describes the on-going synthesis and reactivity of Np(OAr)3 (Ar = 2,6-di-tert-butylphenoxide) utilizing Np[[eta]4-Me2NC(H)C6H5]3 as a Np(III) starting material. The coordination and oxidation chemistry is explored with [nBu4N]N3, (C6H5CO)2O2 and Ph2S2 resulting in a bridged Np(III)/Np(III) azide complex with an outer sphere nBu4N and Np(IV) species, respectively.

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Generation of Tp*2U(N3) from a family of new uranium(III) alkyl complexes

Cited by 13 publications

References 56 publications

Investigation of the Electronic Structure of Aryl-Bridged Dinuclear U(III) and U(IV) Compounds

Investigation of the Electronic Structure of Aryl-Bridged Dinuclear U(III) and U(IV) Compounds

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Synthesis and reactivity of low-valent uranium and neptunium complexes

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