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21.
Vidjayacoumar B Ilango S Ray MJ Chu T Kolpin KB Andreychuk NR Cruz CA Emslie DJ Jenkins HA Britten JF 《Dalton transactions (Cambridge, England : 2003)》2012,41(26):8175-8189
A rigid NSN-donor proligand, 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylthioxanthene (H(2)[TXA(2)], 1) was prepared by palladium-catalyzed coupling of 2,6-diisopropylaniline with 4,5-dibromo-2,7-di-tert-butyl-9,9-dimethylthioxanthene. Deprotonation of 1 using (n)BuLi provided Li(2)(DME)(2)[TXA(2)] (2), and subsequent reaction with UCl(4) afforded [Li(DME)(3)][(TXA(2))UCl(3)] (4). The analogous NON-donor ligated complex [(XA(2))UCl(3)K(DME)(3)] [3; XA(2) = 4,5-bis(2,6-diisopropylanilino)-2,7-di-tert-butyl-9,9-dimethylxanthene] was prepared by the reaction of K(2)(DME)(x)[XA(2)] with UCl(4). A cyclic voltammogram (CV) of 3 in THF/[NBu(4)][B(C(6)F(5))(4)] at 200 mV s(-1) showed an irreversible reduction to uranium(III) at E(pc) = -2.46 V versus FeCp(2)(0/+1), followed by a product wave at E(1/2) = -1.83 V. Complex 4 also underwent irreversible reduction to uranium(iii) [E(pc) = -2.56 V], resulting in an irreversible product peak at E(pa) = -1.83 V. One-electron reduction of complexes 3 and 4 using K(naphthalenide) under an argon atmosphere in DME yielded 6-coordinate [(XA(2))UCl(DME)] (5) and the thermally unstable 7-coordinate [(TXA(2))U(DME)Cl(2)Li(DME)(2)] (6), respectively. The U-S distances in 4 and 6 are uncommonly short, the C-S-U angles are unusually acute, and the thioxanthene backbone of the TXA(2) ligand is significantly bent. By contrast, the xanthene backbone in XA(2) complexes 3 and 5 is planar. However, κ(3)-coordination and an approximately meridional arrangement of the ancillary ligand donor atoms is maintained in all complexes. DFT and Atoms in Molecules (AIM) calculations were carried out on 3, 4, 5, 6, [(XA(2))UCl(3)](-) (3B), [(TXA(2))UCl(2)(DME)](-) (6B) and [(TXA(2))UCl(DME)] (6C) to probe the extent of covalency in U-SAr(2) bonding relative to U-OAr(2) bonding. 相似文献
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S. F. Biagi M. Bourquin A. J. Britten R. M. Brown H. J. Burckhart A. A. Carter Ch. Doré P. Extermann M. Gailloud C. N. P. Gee W. M. Gibson J. C. Gordon R. J. Gray P. Igo-Kemenes P. Jacot-Guillarmod W. C. Louis T. Modis Ph. Rosselet B. J. Saunders P. Schirato H. W. Siebert V. J. Smith K. -P. Streit J. J. Thresher S. N. Tovey R. Weill 《Zeitschrift fur Physik C Particles and Fields》1985,28(2):175-185
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Bulten HJ Anthony PL Arnold RG Arrington J Beise EJ Belz E van Bibber K Bosted PE van den Brand JF Chapman MS Coulter KP Dietrich FS Ent R Epstein M Filippone BW Gao H Gearhart RA Geesaman DF Hansen J Holt RJ Jackson HE Jones CE Keppel CE Kinney E Kuhn SE Lee K Lorenzon W Lung A Makins NC Margaziotis DJ McKeown RD Milner RG Mueller B Napolitano J Nelson J O'Neill TG Papavassiliou V Petratos GG Potterveld DH Rock SE Spengos M Szalata ZM Tao LH White JL Zeidman B 《Physical review letters》1995,74(24):4775-4778
25.
High-efficiency fused-silica transmission gratings 总被引:2,自引:0,他引:2
We describe the design, fabrication, and performance of high-efficiency transmission gratings fabricated in bulk fused silica for use in high-power ultraviolet laser systems. The gratings exhibit a diffraction efficiency of 94% in order m=-1 and a damage threshold greater than 13>J/cm( 2) for 3-ns pulses at 351 nm. Model calculations and experimental measurements are in good agreement. 相似文献
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Surfactants can be introduced into the environment through wastewater or by direct contamination. Understanding the fate and transport of surfactants in the environment is important in assessing their role as pollutants. Humic substances are complex heterogeneous mixtures of decomposition products of natural organic materials. They are environmentally important because they are known to solubilize and transport organic pollutants. Therefore humic substances are likely to affect the environmental fate of surfactants. Diffusion coefficients measured with pulsed-field gradient nuclear magnetic resonance spectroscopy are used in this study to examine the intermolecular interactions of the surfactants sodium dodecyl sulfate (SDS) and cetyltrimethylammonium bromide (CTAB) in the presence of various humic substances. These results indicate that humic substances enhance the aggregation of SDS prior to micellization with a more pronounced effect observed for the more hydrophobic humic materials. The positively charged surfactant CTAB forms stable ion pairs with the humic substances. 相似文献
30.
The simultaneous determination of Cd, Cu, Pb and Zn in lead and zinc concentrates by fundamental, second-harmonic and linear-sweep a.c. and pulse polarographic methods is described. Calibration curves are linear over wide concentration ranges, so that both major and minor trace constituents can be determined in the same experiment; thus the polarographic method is highly competitive with atomic absorption spectrometry (a.a.s.). Conventional a.c. polarography and a.a.s. were compared in the first instance with conservative instrumentation. More sophisticated polarographic methods were then utilized; with the phase-selective linear sweep a.c. (fundamental- and second-harmonic) methods the four elements were determined simultaneously from voltammograms obtained in less than 20 s down to the 10-6-10-7M concentration range. 相似文献