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21.
Conrad A. P. Goodwin Jing Su Thomas E. Albrecht‐Schmitt Anastasia V. Blake Enrique R. Batista Scott R. Daly Stefanie Dehnen William J. Evans Andrew J. Gaunt Stosh A. Kozimor Niels Lichtenberger Brian L. Scott Ping Yang 《Angewandte Chemie (Weinheim an der Bergstrasse, Germany)》2019,131(34):12050-12050
22.
M. J. Jackson C. Gilligan A. V. Davies R. Britton J. I. Friese L. R. Greenwood B. D. Pierson Z. S. Finch B. N. Gartman D. Dry I. May N. C. Smythe A. J. Gaunt E. R. Thomas K. E. Roberts N. K. Harward K. J. Thomas P. T. Woody P. Zhao 《Journal of Radioanalytical and Nuclear Chemistry》2018,318(1):107-115
Samarium-153 (\({}^{153}\hbox {Sm}\)) is a short-lived radionuclide that decays to stable europium-153 via beta emission, with subsequent de-excitation via gamma emission and internal conversion. Historical measurements of \({}^{153}\hbox {Sm}\) by gamma spectrometry and beta liquid scintillation counting have shown a low bias compared to beta proportional counting. In order to investigate this, four national laboratories jointly conducted an experimental inter-comparison exercise on a certified \({}^{153}\hbox {Sm}\) sample, created from neutron activation of samarium-152. Radiometric measurements were conducted using gamma spectrometry, liquid scintillation counting, gas proportional counting, and passivated implanted planar silicon detectors and compared across the four institutions against the certified value. The results from this experiment are presented together with a number of conclusions which suggest that the current published cumulative fission yield for \({}^{153}\hbox {Sm}\), as used by many laboratories, is approximately 15% high and is the likely cause of the previously observed bias. 相似文献
23.
Selective Reductive Elimination at Alkyl Palladium(IV) by Dissociative Ligand Ionization: Catalytic C(sp3)−H Amination to Azetidines 下载免费PDF全文
Manuel Nappi Chuan He William G. Whitehurst Ben G. N. Chappell Prof. Dr. Matthew J. Gaunt 《Angewandte Chemie (International ed. in English)》2018,57(12):3178-3182
A palladium(II)‐catalyzed γ‐C?H amination of cyclic alkyl amines to deliver highly substituted azetidines is reported. The use of a benziodoxole tosylate oxidant in combination with AgOAc was found to be crucial for controlling a selective reductive elimination pathway to the azetidines. The process is tolerant of a range of functional groups, including structural features derived from chiral α‐amino alcohols, and leads to the diastereoselective formation of enantiopure azetidines. 相似文献
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25.
The geometric and electronic structures of the title complexes have been studied using scalar relativistic, gradient-corrected density functional theory. Extension of our previous work on six-coordinate M[N(EPH 2) 2] 3 (M = La, Ce, U, Pu; E = O, S, Se, Te), models for the experimentally characterized M[N(EP (i)Pr 2) 2] 3, yields converged geometries for all of the other 4f and 5f metals studied and for all four group 16 elements. By contrast, converged geometries for nine-coordinate M[N(EPPh 2) 2] 3 are obtained only for E = S and Se. Comparison of the electronic structures of six- and nine-coordinate M[N(EPH 2) 2] 3 suggests that coordination of the N atoms produces only minor changes in the metal-chalcogen interactions. Six-coordinate Eu[N(EPH 2) 2] 3 and Am[N(EPH 2) 2] 3 with the heavier group 16 donors display geometric and electronic properties rather different from those of the other members of the 4f and 5f series, in particular, longer than expected Eu-E and Am-E bond lengths, smaller reductions in charge difference between M and E down group 16, and larger f populations. The latter are interpreted not as evidence of f-based metal-ligand covalency but rather as being indicative of ionic metal centers closer to M (II) than M (III). The Cm complexes are found to be very ionic, with very metal-localized f orbitals and Cm (III) centers. The implications of the results for the separation of the minor actinides from nuclear wastes are discussed, as is the validity of using La (III)/U (III) comparisons as models for minor actinide/Eu systems. 相似文献
26.
CM Silva MF Duarte ML Mira MH Florêncio K Versluis AJ Heck 《Rapid communications in mass spectrometry : RCM》1999,13(12):1098-1103
Fast atom bombardment, combined with high-energy collision-induced tandem mass spectrometry, has been used to investigate gas-phase metal-ion interactions with captopril, enalaprilat and lisinopril, all angiotensin-converting enzyme inhibitors.Suggestions for the location of metal-binding sites are presented. For captopril, metal binding occurs most likely at both the sulphur and the nitrogen atom. For enalaprilat and lisinopril, binding preferably occurs at the amine nitrogen. Copyright 1999 John Wiley & Sons, Ltd. 相似文献
27.
Jing Su Thibault Cheisson Alex McSkimming Conrad A. P. Goodwin Ida
M. DiMucci Thomas Albrecht-Schnzart Brian L. Scott Enrique R. Batista Andrew J. Gaunt Stosh A. Kozimor Ping Yang Eric J. Schelter 《Chemical science》2021,12(40):13343
There is significant interest in ligands that can stabilize actinide ions in oxidation states that can be exploited to chemically differentiate 5f and 4f elements. Applications range from developing large-scale actinide separation strategies for nuclear industry processing to carrying out analytical studies that support environmental monitoring and remediation efforts. Here, we report syntheses and characterization of Np(iv), Pu(iv) and Am(iii) complexes with N-tert-butyl-N-(pyridin-2-yl)hydroxylaminato, [2-(tBuNO)py]−(interchangeable hereafter with [(tBuNO)py]−), a ligand which was previously found to impart remarkable stability to cerium in the +4 oxidation state. An[(tBuNO)py]4 (An = Pu, 1; Np, 2) have been synthesized, characterized by X-ray diffraction, X-ray absorption, 1H NMR and UV-vis-NIR spectroscopies, and cyclic voltammetry, along with computational modeling and analysis. In the case of Pu, oxidation of Pu(iii) to Pu(iv) was observed upon complexation with the [(tBuNO)py]− ligand. The Pu complex 1 and Np complex 2 were also isolated directly from Pu(iv) and Np(iv) precursors. Electrochemical measurements indicate that a Pu(iii) species can be accessed upon one-electron reduction of 1 with a large negative reduction potential (E1/2 = −2.26 V vs. Fc+/0). Applying oxidation potentials to 1 and 2 resulted in ligand-centered electron transfer reactions, which is different from the previously reported redox chemistry of UIV[(tBuNO)py]4 that revealed a stable U(v) product. Treatment of an anhydrous Am(iii) precursor with the [(tBuNO)py]− ligand did not result in oxidation to Am(iv). Instead, the dimeric complex [AmIII(μ2-(tBuNO)py)((tBuNO)py)2]2 (3) was isolated. Complex 3 is a rare example of a structurally characterized non-aqueous Am-containing molecular complex prepared using inert atmosphere techniques. Predicted redox potentials from density functional theory calculations show a trivalent accessibility trend of U(iii) < Np(iii) < Pu(iii) and that the higher oxidation states of actinides (i.e., +5 for Np and Pu and +4 for Am) are not stabilized by [2-(tBuNO)py]−, in good agreement with experimental observations.The coordination modes and electronic properties of a strongly coordinating hydroxylaminato ligand with Np, Pu and Am were investigated.Complexes were characterized by a range of experimental and computational techniques. 相似文献
28.
Beck EM Grimster NP Hatley R Gaunt MJ 《Journal of the American Chemical Society》2006,128(8):2528-2529
A palladium catalyzed C-H bond functionalization system that operates under ambient and aerobic conditions can be used to alkenylate pyrroles with control of regioselectivty. A steric and electronic control strategy can be used to influence positional control in the C-H bond functionalization process that results in either the C2 or C3 alkenylated products. Air, molecular oxygen, or tBuOOBz can be used as reoxidant in this mild process, and the reaction works on a range of substrates. Finally a catalytic aerobic annulation strategy is described that can be controlled to produce cyclization at either the C2 or C3 positions, thus forming diverse pyrrole products. 相似文献
29.
SD Reilly AJ Gaunt BL Scott G Modolo M Iqbal W Verboom MJ Sarsfield 《Chemical communications (Cambridge, England)》2012,48(78):9732-9734
Complexation of Pu(iv) with TMDGA, TEDGA, and TODGA diglycolamide ligands was followed by vis-NIR spectroscopy. A crystal structure determination reveals that TMDGA forms a 1?:?3 homoleptic Pu(iv) complex with the nitrate anions forced into the outer coordination sphere. 相似文献
30.
DD Schnaars AJ Gaunt TW Hayton MB Jones I Kirker N Kaltsoyannis I May SD Reilly BL Scott G Wu 《Inorganic chemistry》2012,51(15):8557-8566
A series of tetravalent An(IV) complexes with a bis-phenyl β-ketoiminate N,O donor ligand has been synthesized with the aim of identifying bonding trends and changes across the actinide series. The neutral molecules are homoleptic with the formula An((Ar)acnac)(4) (An = Th (1), U (2), Np (3), Pu (4); (Ar)acnac = ArNC(Ph)CHC(Ph)O; Ar = 3,5-(t)Bu(2)C(6)H(3)) and were synthesized through salt metathesis reactions with actinide chloride precursors. NMR and electronic absorption spectroscopy confirm the purity of all four new compounds and demonstrate stability in both solution and the solid state. The Th, U, and Pu complexes were structurally elucidated by single-crystal X-ray diffraction and shown to be isostructural in space group C2/c. Analysis of the bond lengths reveals shortening of the An-O and An-N distances arising from the actinide contraction upon moving from 1 to 2. The shortening is more pronounced upon moving from 2 to 4, and the steric constraints of the tetrakis complexes appear to prevent the enhanced U-O versus Pu-O orbital interactions previously observed in the comparison of UI(2)((Ar)acnac)(2) and PuI(2)((Ar)acnac)(2) bis-complexes. Computational analysis of models for 1, 2, and 4 (1a, 2a, and 4a, respectively) concludes that both the An-O and the An-N bonds are predominantly ionic for all three molecules, with the An-O bonds being slightly more covalent. Molecular orbital energy level diagrams indicate the largest 5f-ligand orbital mixing for 4a (Pu), but spatial overlap considerations do not lead to the conclusion that this implies significantly greater covalency in the Pu-ligand bonding. QTAIM bond critical point data suggest that both U-O/U-N and Pu-O/Pu-N are marginally more covalent than the Th analogues. 相似文献