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121.
Dr. Michael Bodensteiner Prof. Dr. Alexey Y. Timoshkin Dr. Eugenia V. Peresypkina Dr. Ulf Vogel Prof. Dr. Manfred Scheer 《Chemistry (Weinheim an der Bergstrasse, Germany)》2013,19(3):957-963
The reaction of [{(CO)5W}PRH2] (R=H, Ph) with H3Al ? NR3 (R=Et, Me) leads to the formation of four‐membered heterocyclic compounds [({(CO)5W}P(H)AlH ? NEt3)2] and [({(CO)5W}PhPAlH ? NMe3)2]. Upon dissolving the solid compounds, fast equilibria between the isomers are observed on the NMR timescale. Further insight into the stability and reactivity of the isomers was gained by applying theoretical methods. DFT calculations predict that hydrogen elimination in the case of [({(CO)5W}PhPAlH ? NMe3)2] may be reversible. 相似文献
122.
We study the adsorption of homogeneous or heterogeneous polymers onto heterogeneous planar surfaces with exponentially decaying site-site correlations, using a variational reference system approach. As a main result, we derive simple equations for the adsorption-desorption transition line. We show that it is preferable to have a small amount of strongly adsorbing sites or monomers rather than a greater amount of weakly adsorbing ones. The results are discussed with respect to their implications for the physics of molecular recognition. 相似文献
123.
Comparative computational studies of reaction mechanisms of formation and unimolecular hydrogen evolution from alkali metal amidoboranes MNH2BH3 and their carbon analogs MC2H5 (M = Li – Cs) were performed at the B3LYP/def2‐TZVPPD level of theory. Transition states (TS) for the consecutive dehydrogenation reactions were optimized. In contrast to endergonic dehydrogenation of carbon analogs, dehydrogenation reactions of alkali metal amidoboranes are exergonic at room temperature. The nature of the alkali metal does not significantly affect the thermodynamic characteristics and activation energies of unimolecular gas phase dehydrogenation reactions. The influence of the alkali metal is qualitatively similar for amidoboranes and their carbon analogs. 相似文献
124.
Dianionic Titanyl and Vanadyl (Cation+)2[MIVO(Pc4−)]2− Phthalocyanine Salts Containing Pc4− Macrocycles 下载免费PDF全文
Dr. Dmitri V. Konarev Dr. Alexey V. Kuzmin Dr. Salavat S. Khasanov Alexey L. Litvinov Dr. Akihiro Otsuka Prof. Hideki Yamochi Prof. Hiroshi Kitagawa Prof. Rimma N. Lyubovskaya 《化学:亚洲杂志》2018,13(12):1552-1560
In this study, the titanyl and vanadyl phthalocyanine (Pc) salts (Bu4N+)2[MIVO(Pc4?)]2? (M=Ti, V) and (Bu3MeP+)2[MIVO(Pc4?)]2? (M=Ti, V) with [MIVO(Pc4?)]2? dianions were synthesized and characterized. Reduction of MIVO(Pc2?) carried out with an excess of sodium fluorenone ketyl in the presence of Bu4N+ or Bu3MeP+ is exclusive to the phthalocyanine centers, forming Pc4? species. During reduction, the metal +4 charge did not change, implying that Pc is an non‐innocent ligand. The Pc negative charge increase caused the C?N(pyr) bonds to elongate and the C?N(imine) bonds to alternate, thus increasing the distortion of Pc. Jahn–Teller effects are significant in the [eg(π*)]2 dianion ground state and can additionally distort the Pc macrocycles. Blueshifts of the Soret and Q‐bands were observed in the UV/Vis/NIR when MIVO(Pc2?) was reduced to [MIVO(Pc . 3?)] . ? and [MIVO(Pc4?)]2?. From magnetic measurements, [TiIVO(Pc4?)]2? was found to be diamagnetic and (Bu4N+)2[VIVO(Pc4?)]2? and (Bu3MeP+)2[VIVO(Pc4?)]2? were found to have magnetic moments of 1.72–1.78 μB corresponding to an S=1/2 spin state owing to VIV electron spin. As a result, two latter salts show EPR signals with VIV hyperfine coupling. 相似文献
125.
Sergey G. Arkhipov Denis A. Rychkov Alexey M. Pugachev Elena V. Boldyreva 《Acta Crystallographica. Section C, Structural Chemistry》2015,71(7):584-592
Crystals of maleates of three amino acids with hydrophobic side chains [L‐leucenium hydrogen maleate, C6H14NO2+·C4H3O4−, (I), L‐isoleucenium hydrogen maleate hemihydrate, C6H14NO2+·C4H3O4−·0.5H2O, (II), and L‐norvalinium hydrogen maleate–L‐norvaline (1/1), C5H11NO2+·C4H3O4−·C5H12NO2, (III)], were obtained. The new structures contain C22(12) chains, or variants thereof, that are a common feature in the crystal structures of amino acid maleates. The L‐leucenium salt is remarkable due to a large number of symmetrically non‐equivalent units (Z′ = 3). The L‐isoleucenium salt is a hydrate despite the fact that L‐isoleucine is a nonpolar hydrophobic amino acid (previously known amino acid maleates formed hydrates only with lysine and histidine, which are polar and hydrophilic). The L‐norvalinium salt provides the first example where the dimeric cation L‐Nva...L‐NvaH+ was observed. All three compounds have layered noncentrosymmetric structures. Preliminary tests have shown the presence of the second harmonic generation (SGH) effect for all three compounds. 相似文献
126.
Alexey Marchuk Florian J. Pucher Friedrich W. Karau Prof. Dr. Wolfgang Schnick 《Angewandte Chemie (International ed. in English)》2014,53(9):2469-2472
Phosphorus nitride imide, PN(NH), is of great scientific importance because it is isosteric with silica (SiO2). Accordingly, a varied structural diversity could be expected. However, only one polymorph of PN(NH) has been reported thus far. Herein, we report on the synthesis and structural investigation of the first high‐pressure polymorph of phosphorus nitride imide, β‐PN(NH); the compound has been synthesized using the multianvil technique. By adding catalytic amounts of NH4Cl as a mineralizer, it became possible to grow single crystals of β‐PN(NH), which allowed the first complete structural elucidation of a highly condensed phosphorus nitride from single‐crystal X‐ray diffraction data. The structure was confirmed by FTIR and 31P and 1H solid‐state NMR spectroscopy. We are confident that high‐pressure/high‐temperature reactions could lead to new polymorphs of PN(NH) containing five‐fold‐ or even six‐fold‐coordinated phosphorus atoms and thus rivalling or even surpassing the structural variety of SiO2. 相似文献
127.
Macromolecule Loading into Spherical,Elliptical, Star‐Like and Cubic Calcium Carbonate Carriers 下载免费PDF全文
Dr. Bogdan V. Parakhonskiy Dr. Alexey M. Yashchenok Dr. Senem Donatan Dr. Dmitry V. Volodkin Dr. Francesco Tessarolo Prof. Renzo Antolini Prof. Helmuth Möhwald Prof. Andre G. Skirtach 《Chemphyschem》2014,15(13):2817-2822
We fabricated calcium carbonate particles with spherical, elliptical, star‐like and cubical morphologies by varying relative salt concentrations and adding ethylene glycol as a solvent to slow down the rate of particle formation. The loading capacity of particles of different isotropic (spherical and cubical) and anisotropic (elliptical and star‐like) geometries is investigated, and the surface area of such carriers is analysed. Potential applications of such drug delivery carriers are highlighted. 相似文献
128.
Yury Rodimkov Evgeny Efimenko Valentin Volokitin Elena Panova Alexey Polovinkin Iosif Meyerov Arkady Gonoskov 《Entropy (Basel, Switzerland)》2021,23(1)
When entering the phase of big data processing and statistical inferences in experimental physics, the efficient use of machine learning methods may require optimal data preprocessing methods and, in particular, optimal balance between details and noise. In experimental studies of strong-field quantum electrodynamics with intense lasers, this balance concerns data binning for the observed distributions of particles and photons. Here we analyze the aspect of binning with respect to different machine learning methods (Support Vector Machine (SVM), Gradient Boosting Trees (GBT), Fully-Connected Neural Network (FCNN), Convolutional Neural Network (CNN)) using numerical simulations that mimic expected properties of upcoming experiments. We see that binning can crucially affect the performance of SVM and GBT, and, to a less extent, FCNN and CNN. This can be interpreted as the latter methods being able to effectively learn the optimal binning, discarding unnecessary information. Nevertheless, given limited training sets, the results indicate that the efficiency can be increased by optimizing the binning scale along with other hyperparameters. We present specific measurements of accuracy that can be useful for planning of experiments in the specified research area. 相似文献
129.
Ryding MJ Ruusuvuori K Andersson PU Zatula AS McGrath MJ Kurtén T Ortega IK Vehkamäki H Uggerud E 《The journal of physical chemistry. A》2012,116(20):4902-4908
Molecular cluster ions H(+)(H(2)O)(n), H(+)(pyridine)(H(2)O)(n), H(+)(pyridine)(2)(H(2)O)(n), and H(+)(NH(3))(pyridine)(H(2)O)(n) (n = 16-27) and their reactions with ammonia have been studied experimentally using a quadrupole-time-of-flight mass spectrometer. Abundance spectra, evaporation spectra, and reaction branching ratios display magic numbers for H(+)(NH(3))(pyridine)(H(2)O)(n) and H(+)(NH(3))(pyridine)(2)(H(2)O)(n) at n = 18, 20, and 27. The reactions between H(+)(pyridine)(m)(H(2)O)(n) and ammonia all seem to involve intracluster proton transfer to ammonia, thus giving clusters of high stability as evident from the loss of several water molecules from the reacting cluster. The pattern of the observed magic numbers suggest that H(+)(NH(3))(pyridine)(H(2)O)(n) have structures consisting of a NH(4)(+)(H(2)O)(n) core with the pyridine molecule hydrogen-bonded to the surface of the core. This is consistent with the results of high-level ab initio calculations of small protonated pyridine/ammonia/water clusters. 相似文献
130.
Yuriy A. Zhabanov Alexey V. Eroshin Igor V. Ryzhov Ilya A. Kuzmin Daniil N. Finogenov Pavel A. Stuzhin 《Molecules (Basel, Switzerland)》2021,26(10)
The Knudsen effusion method with mass spectrometric control of the vapor composition was used to study the possibility of a congruent transition to the gas phase and to estimate the enthalpy of sublimation of metal-free tetrakis(1,2,5-thiadiazolo)porphyrazine and its nickel complex (H2TTDPz and NiTTDPz, respectively). The geometrical and electronic structure of H2TTDPz and NiTTDPz in ground and low-lying excited electronic states were determined by DFT calculations. The electronic structure of NiTTDPz was studied by the complete active space (CASSCF) method, following accounting dynamic correlation by multiconfigurational quasi-degenerate second-order perturbation theory (MCQDPT2). A geometrical structure of D2h and D4h symmetry was obtained for H2TTDPz and NiTTDPz, respectively. According to data obtained by the MCQDPT2 method, the nickel complex possesses the ground state 1A1g, and the wave function of the ground state has the form of a single determinant. Electronic absorption and vibrational (IR and resonance Raman) spectra of H2TTDPz and NiTTDPz were studied experimentally and simulated theoretically. 相似文献