Expanding the Family of Uranium(III) Alkyls: Synthesis and Characterization of Mixed‐Ligand Derivatives

Matson, Ellen M.; Kiernicki, John J.; Fanwick, Phillip E.; Bart, Suzanne C.

doi:10.1002/ejic.201501251

Cited by 17 publications

(18 citation statements)

References 35 publications

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“…complexes. [20,23,[26][27][28]30,31] In contrast, the visible region for 2 and 2-Phpz displays broad, weak absorptions as expected for uranium(IV) species, similar to yellow Tp* 2 U(η 2 -S 2 ).…”

Section: Preparation Of Kphpzmentioning

confidence: 68%

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Synthesis and characterization of hydrotris(3-phenylpyrazolyl)borate ligands on low-valent uranium

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Treating both UI 3 (THF) 4 and UI 4 (dioxane) 2 with one equivalent of potassium hydrotris(3phenylpyrazolyl)borate, KTp Ph , resulted in the formation of new low-valent uranium derivatives, Tp Ph UI 2 (THF) 2 (1) and Tp Ph UI 3 (2), respectively. Spectroscopic characterization of these species shows that the Tp Ph ligand is 1,2-borotropically shifted, causing one phenyl group to point towards the B-H rather than the uranium center. Derivatization of these materials was possible via salt metathesis reactions, and in each case, the borotropically shifted phenyl group is maintained. Treating trivalent 1 with one equivalent of potassium phenoxide, KOPh, afforded trivalent Tp Ph U(OPh)I(THF) 2 (1-OPh), whereas, a uranium(IV) derivative, Tp Ph UI 2 (Phpz)(THF) (2-Phpz), was synthesized by treating 2 with potassium 3-phenylpyrazolide, KPhpz. All compounds were characterized by 1 H and 11 B NMR, infrared, and electronic absorption spectroscopies, and where possible, X-ray crystallography.

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Section: Preparation Of Kphpzmentioning

confidence: 68%

“…[19] In previous work from our group, we have demonstrated the utility of the Tp* ligand to support low-valent uranium. [18,[20][21][22][23][24][25][26][27][28][29][30][31] However, the steric protection of this ligand is limited due to the small size of the methyl groups.…”

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Synthesis and characterization of hydrotris(3-phenylpyrazolyl)borate ligands on low-valent uranium

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“…[26][27][28][29][30][31] The thermalb ehaviour of several LnTp 3 compounds has also been investigated by thermogravimetric/differential thermala nalysis( TG/DTG) and differential scanning calorimetry (DSC) techniques. [32] Some compoundso ft etravalent thorium and uranium with the unsubstituted Tp ligand have been reportedi nt he literature, [33][34][35][36][37][38][39][40] but only little information on compounds of transuranic elements is available. [41,42] The absorption spectrum of UTp 3 [43] and the magnetic behaviour of UTp 3 [44,45] and PuTp 3 [46,47] prepared with the unsubstituted Tp ligand have been reported more recently.T he magnetic properties of the latter two compounds have also been analysed by relativistic multireference quantum chemicalc alculations.…”

Section: Introductionmentioning

confidence: 99%

“…[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.…”

Section: Introductionmentioning

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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Expanding the Family of Uranium(III) Alkyls: Synthesis and Characterization of Mixed‐Ligand Derivatives

Cited by 17 publications

References 35 publications

Synthesis and characterization of hydrotris(3-phenylpyrazolyl)borate ligands on low-valent uranium

Synthesis and characterization of hydrotris(3-phenylpyrazolyl)borate ligands on low-valent uranium

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Synthesis and reactivity of low-valent uranium and neptunium complexes

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