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91.
Sarazin Y Hughes DL Kaltsoyannis N Wright JA Bochmann M 《Journal of the American Chemical Society》2007,129(4):881-894
The reaction of thallium ethoxide with [H(OEt2)2][H2N{B(C6F5)3}2] in diethyl ether afforded [Tl(OEt2)3][H2N{B(C6F5)3}2] (2a), [Tl(OEt2)4][H2N{B(C6F5)3}2] (2b), or [Tl(OEt2)2][H2N{B(C6F5)3}2].CH2Cl2 (2c), depending on the reaction conditions. The dication in the hydrolysis product [Tl4(mu3-OH)2][H2N{B(C6F5)3}2]2.4CH2Cl2 consists of two bridging and two terminal Tl+ ions bound to triply bridging hydroxides. Heating Et2O complexes in toluene afforded [Tl(eta6-toluene)n][H2N{B(C6F5)3}2] (4, n = 2, 3), while C6Me6 addition gave the first thallium-C6Me6 adduct, [Tl(eta6-C6Me6)2][H2N{B(C6F5)3}2].1.5CH2Cl2 (5a), a bent sandwich complex with very short Tl...centroid distances. These arene complexes show no close contacts between cations and anions. Displacement of toluene ligands by ferrocene gave [Tl2(FeCp2)3][H2N{B(C6F5)3}2]2.5CH2Cl2 (6) which contains the multidecker cations [Tl(FeCp2)]+ and [Tl(FeCp2)2]+ in a 1:1 ratio. By contrast, decamethylferrocene leads to electron transfer; the isolable thallium-ferrocene complexes may therefore be viewed as precursor complexes for this redox step. With 18-crown-6 the complexes [Tl(18-crown-6)2][H2N{B(C6F5)3}2] (11a) and [Tl(18-crown-6)][H2N{B(C6F5)3}2].2CH2Cl2 (11b) were isolated. The structure of the latter shows an eight-coordinate thallium ion, where the coordination to the six oxygen donors in equatorial positions is completed by axial contacts to two F atoms of the counter anions. The bonding between thallium(I) and arenes was explored by density-functional theory (DFT) calculations. The optimized geometry of [Tl(tol)3]+ converged to a structure very similar to that obtained experimentally. Calculations on [Tl(C6Me6)2]+ (5b) to establish whether a linear or bent geometry is the most stable revealed a very flat potential-energy surface for distortions of the Ctr(3)-Tl-Ctr(4) angle. Overall, there is very little energetic preference for one particular geometry over another above about 140 degrees , in good agreement with the crystallographic geometry. The calculated Tl-arene interaction energies increase from 73.7 kJ mol-1 for toluene to 121.7 kJ mol-1 for C6Me6. 相似文献
92.
Häller LJ Kaltsoyannis N Sarsfield MJ May I Cornet SM Redmond MP Helliwell M 《Inorganic chemistry》2007,46(12):4868-4875
Phosphinimine ligands (Cy3PNH) readily react with UO2Cl2(THF)3 (THF=tetrahydrofuran) to give UO2Cl2(Cy3PNH)2, which contains strong U-N interactions and exists as cis and trans isomers in the solid and solution state. Solution NMR experiments and computational analysis both support the trans form as the major isomer in solution, although the cis isomer becomes more stabilized with an increase in the dielectric constant of the solvent. Mayer bond orders, energy decomposition analysis, and examination of the molecular orbitals and total electron densities support a more covalent bonding interaction in the U-NHPCy3 bond compared with the analogous bond of the related U-OPCy3 compounds. 相似文献
93.
Evans WJ Lee DS Ziller JW Kaltsoyannis N 《Journal of the American Chemical Society》2006,128(43):14176-14184
The [Z(2)Ln(THF)](2)(mu-eta(2)():eta(2)()-N(2)) complexes (Z = monoanionic ligand) generated by reduction of dinitrogen with trivalent lanthanide salts and alkali metals are strong reductants in their own right and provide another option in reductive lanthanide chemistry. Hence, lanthanide-based reduction chemistry can be effected in a diamagnetic trivalent system using the dinitrogen reduction product, [(C(5)Me(5))(2)(THF)La](2)(mu-eta(2)():eta(2)()-N(2)), 1, readily obtained from [(C(5)Me(5))(2)La][BPh(4)], KC(8), and N(2). Complex 1 reduces phenazine, cyclooctatetraene, anthracene, and azobenzene to form [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(12)H(8)N(2))], 2, (C(5)Me(5))La(C(8)H(8)), 3, [(C(5)Me(5))(2)La](2)[mu-eta(3):eta(3)-(C(14)H(10))], 4, and [(C(5)Me(5))La(mu-eta(2)-(PhNNPh)(THF)](2), 5, respectively. Neither stilbene nor naphthalene are reduced by 1, but 1 reduces CO to make the ketene carboxylate complex {[(C(5)Me(5))(2)La](2)[mu-eta(4)-O(2)C-C=C=O](THF)}(2), 6, that contains CO-derived carbon atoms completely free of oxygen. 相似文献
94.
Vinzenz Bildstein Roman Gernh?user Thorsten Kr?ll Reiner Krücken Kathrin Wimmer Piet Van Duppen Mark Huyse Nikolas Patronis Riccardo Raabe 《The European Physical Journal A - Hadrons and Nuclei》2012,48(6):1-10
The potential barrier impeding the spontaneous emission of protons in the proton radioactive nuclei is calculated as the sum of nuclear, Coulomb and centrifugal contributions. The nuclear part of the proton-nucleus interaction potential is obtained in the energy density formalism using the Skyrme effective interaction that results into a simple algebraic expression. The half-lives of the proton emitters are calculated for the different Skyrme sets within the improved WKB framework. The results are found to be in reasonable agreement with the earlier results obtained for more complicated calculations involving finite-range interactions. 相似文献
95.
Yardibi T Li J Stoica P Zawodny NS Cattafesta LN 《The Journal of the Acoustical Society of America》2010,127(5):2920-2931
Microphone arrays are commonly used for noise source localization and power estimation in aeroacoustic measurements. The delay-and-sum (DAS) beamformer, which is the most widely used beamforming algorithm in practice, suffers from low resolution and high sidelobe level problems. Therefore, deconvolution approaches, such as the deconvolution approach for the mapping of acoustic sources (DAMAS), are often used for extracting the actual source powers from the contaminated DAS results. However, most deconvolution approaches assume that the sources are uncorrelated. Although deconvolution algorithms that can deal with correlated sources, such as DAMAS for correlated sources, do exist, these algorithms are computationally impractical even for small scanning grid sizes. This paper presents a covariance fitting approach for the mapping of acoustic correlated sources (MACS), which can work with uncorrelated, partially correlated or even coherent sources with a reasonably low computational complexity. MACS minimizes a quadratic cost function in a cyclic manner by making use of convex optimization and sparsity, and is guaranteed to converge at least locally. Simulations and experimental data acquired at the University of Florida Aeroacoustic Flow Facility with a 63-element logarithmic spiral microphone array in the absence of flow are used to demonstrate the performance of MACS. 相似文献
96.
Shouchuan Hu Nikolas S. Papageorgiou 《Nonlinear Analysis: Theory, Methods & Applications》2010,73(12):3675-883
We consider a nonlinear periodic equation driven by the scalar p-Laplacian and with a Caratheodory asymptotically (p−1)-linear nonlinearity. Using variational methods coupled with suitable truncation techniques, we show that the problem has at least two positive solutions. For the semilinear case (p=2), using Morse theory we show that the problem has three distinct positive solutions. 相似文献
97.
Antigoni Cheilari Argyro Vontzalidou Maria Makropoulou Aggeliki K. Meligova Nikolas Fokialakis Sofia Mitakou Michael N. Alexis Nektarios Aligiannis 《Molecules (Basel, Switzerland)》2020,25(23)
As part of our ongoing research on phytoestrogens, we investigated the phytochemical profile and estrogen-like activities of eight extracts from the aerial parts of four Genista species of Greek flora using estrogen-responsive cell lines. Ethyl acetate and methanolic extracts of G. acanthoclada, G. depressa, G. hassertiana, and G. millii were obtained with accelerated solvent extraction and their phytochemical profiles were compared using ultra-high-performance liquid chromatography-high-resolution mass spectrometry (uHPLC-HRMS). Fourteen isoflavonoids, previously isolated from G. halacsyi, were used as reference standards for their identification in the extracts. Thirteen isoflavonoids were detected in both extracts of G. acanthoclada and G. hassertiana, while fewer and far fewer were detected in G. millii and G. depressa, respectively. The ethyl acetate extracts of G. hassertiana and G. acanthoclada displayed 2.45- and 1.79-fold higher, respectively, estrogen-like agonist activity in Ishikawa cells compared to MCF-7 cells at pharmacologically relevant concentrations. Both these extracts, but not that of G. depressa, contained mono- and di-O-β-d-glucosides of genistein as well as the aglycone, all three of which are known to display full estrogen-like activity at lower-than-micromolar concentrations. The possibility of using preparations rich in G. hassertiana and/or G. acanthoclada extracts as a potentially safer substitute for low-dose vaginal estrogen for menopausal symptoms is discussed. 相似文献
98.
99.
100.
The geometric structures of gas-phase Sr(2+) hydrates are calculated quantum chemically by using hybrid (B3LYP) and meta-GGA (TPSS) density functional theory, and a range of thermodynamic data (including sequential bond enthalpies, entropies and free energies for the reactions Sr(2+)(H(2)O)(n-1)+H(2)O→Sr(2+)(H(2)O)(n)) are shown to be in excellent agreement with experiment. When the number of coordinating water molecules exceeds six, such that water begins to occupy the second solvation shell, it is found that detailed analysis based on both geometrical and conformational entropy is required in order to confidently identify the experimentally observed structures. The significant increase in coordination number observed experimentally between the gas- and aqueous-phase species is successfully reproduced, as is the first solvation shell geometry. Inaccurate second shell geometries imply that larger model systems may be required to achieve agreement with experiment. Candidate species for on-going computational studies of the interaction of hydrated Sr(2+) with brucite surfaces have been identified. 相似文献