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311.
312.
Prasenjit Mondal Marta Lovisari Brendan Twamley Aidan R. McDonald 《Angewandte Chemie (International ed. in English)》2020,59(31):13044-13050
In the search for highly reactive oxidants we have identified high‐valent metal–fluorides as a potential potent oxidant. The high‐valent Ni–F complex [NiIII(F)(L)] ( 2 , L=N,N′‐(2,6‐dimethylphenyl)‐2,6‐pyridinedicarboxamidate) was prepared from [NiII(F)(L)]? ( 1 ) by oxidation with selectfluor. Complexes 1 and 2 were characterized by using 1H/19F NMR, UV‐vis, and EPR spectroscopies, mass spectrometry, and X‐ray crystallography. Complex 2 was found to be a highly reactive oxidant in the oxidation of hydrocarbons. Kinetic data and products analysis demonstrate a hydrogen atom transfer mechanism of oxidation. The rate constant determined for the oxidation of 9,10‐dihydroanthracene (k2=29 m ?1 s?1) compared favorably with the most reactive high‐valent metallo‐oxidants. Complex 2 displayed reaction rates 2000–4500‐fold enhanced with respect to [NiIII(Cl)(L)] and also displayed high kinetic isotope effect values. Oxidative hydrocarbon and phosphine fluorination was achieved. Our results provide an interesting direction in designing catalysts for hydrocarbon oxidation and fluorination 相似文献
313.
Dr. Andrey V. Zaytsev Dr. Rachel Bulmer Prof. Valery N. Kozhevnikov Dr. Mark Sims Dr. Giuseppe Modolo Dr. Andreas Wilden Dr. Paul G. Waddell Dr. Andreas Geist Prof. Petra J. Panak Patrik Wessling Dr. Frank W. Lewis 《Chemistry (Weinheim an der Bergstrasse, Germany)》2020,26(2):428-437
The synthesis and evaluation of three novel bis-1,2,4-triazine ligands containing five-membered aliphatic rings are reported. Compared to the more hydrophobic ligands 1 – 3 containing six-membered aliphatic rings, the distribution ratios for relevant f-block metal ions were approximately one order of magnitude lower in each case. Ligand 10 showed an efficient, selective and rapid separation of AmIII and CmIII from nitric acid. The speciation of the ligands with trivalent f-block metal ions was probed using NMR titrations and competition experiments, time-resolved laser fluorescence spectroscopy and X-ray crystallography. While the tetradentate ligands 8 and 10 formed LnIII complexes of the same stoichiometry as their more hydrophobic analogues 2 and 3 , significant differences in speciation were observed between the two classes of ligand, with a lower percentage of the extracted 1:2 complexes being formed for ligands 8 and 10 . The structures of the solid state 1:1 and 1:2 complexes formed by 8 and 10 with YIII, LuIII and PrIII are very similar to those formed by 2 and 3 with LnIII. Ligand 10 forms CmIII and EuIII 1:2 complexes that are thermodynamically less stable than those formed by ligand 3 , suggesting that less hydrophobic ligands form less stable AnIII complexes. Thus, it has been shown for the first time how tuning the cyclic aliphatic part of these ligands leads to subtle changes in their metal ion speciation, complex stability and metal extraction affinity. 相似文献
314.
Phase-distribution data have been generated for two-phase (air-water) flow splitting at an impacting tee junction with a horizontal inlet and inclined outlets. This investigation also considered the possibility of full separation at the junction and the effect of the outlet angle of inclination on partial separation at various inlet conditions. A flow loop with the ability to incline the outlets from horizontal to vertical was constructed. The operating conditions were as follows: test section inside diameter (D) of 13.5 mm, nominal junction pressure (Ps) of 200 kPa (abs), near ambient temperature (Ts), inlet superficial gas velocities (JG1) ranging from 2.0 to 40 m/s, inlet superficial liquid velocities (JL1) ranging from 0.01 to 0.18 m/s, inlet qualities (x1) ranging from 0.1 to 0.9, mass split ratios (W3/W1) from 0 to 1.0, and inlet flow regimes of stratified, wavy, and annular. The data reveal that the degree of maldistribution of the phases depended on the inlet conditions, the mass split ratio at the junction, and the inclination angle of the outlets. 相似文献
315.
Berteloite C Le Picard SD Sims IR Rosi M Leonori F Petrucci R Balucani N Wang X Casavecchia P 《Physical chemistry chemical physics : PCCP》2011,13(18):8485-8501
The reaction between sulfur atoms in the first electronically excited state, S((1)D), and methane (CH(4)), has been investigated in a complementary fashion in (a) crossed-beam dynamics experiments with mass spectrometric detection and time-of-flight (TOF) analysis at two collision energies (30.4 and 33.6 kJ mol(-1)), (b) low temperature kinetics experiments ranging from 298 K down to 23 K, and (c) electronic structure calculations of stationary points and product energetics on the CH(4)S singlet potential energy surface. The rate coefficients for total loss of S((1)D) are found to be very large (ca. 2 × 10(-10) cm(3) molec(-1) s(-1)) down to very low temperatures indicating that the overall reaction is barrier-less. Similar measurements are also performed for S((1)D) + C(2)H(2), and also for this system the rate coefficients are found to be very large (ca. 3 × 10(-10) cm(3) molec(-1) s(-1)) down to very low temperatures. From laboratory angular and TOF distributions at different product masses for the reaction S((1)D) + CH(4), it is found that the only open reaction channel at the investigated collision energies is that leading to SH + CH(3). The product angular, T(θ), and translational energy, P(E'(T)), distributions in the center-of-mass frame are derived. The reaction dynamics are discussed in terms of two different micromechanisms: a dominant long-lived complex mechanism at small and intermediate impact parameters with a strongly polarized T(θ), and a direct pickup-type (stripping) mechanism occurring at large impact parameters with a strongly forward peaked T(θ). Interpretation of the experimental results on the S((1)D) + CH(4) reaction kinetics and dynamics is assisted by high-level theoretical calculations on the CH(4)S singlet potential energy surface. The dynamics of the SH + CH(3) forming channel are compared with those of the corresponding channel (leading to OH + CH(3)) in the related O((1)D) + CH(4) reaction, previously investigated in crossed-beams in other laboratories at comparable collision energies. The possible astrophysical relevance of S((1)D) reactions with hydrocarbons, especially in the chemistry of cometary comae, is discussed. 相似文献
316.
We catalogue the primitive ideals of the Cuntz–Krieger algebra of a row-finite higher-rank graph with no sources. Each maximal tail in the vertex set has an abelian periodicity group of finite rank at most that of the graph; the primitive ideals in the Cuntz–Krieger algebra are indexed by pairs consisting of a maximal tail and a character of its periodicity group. The Cuntz–Krieger algebra is primitive if and only if the whole vertex set is a maximal tail and the graph is aperiodic. 相似文献
317.
Kayla J. Pyper David K. Kempe Jade Y. Jung Li-Hsing J. Loh Nigel Gwini Benjamin D. Lang Brittney S. Newton Jonathan M. Sims Vladimir N. Nesterov Gregory L. Powell 《Journal of Cluster Science》2013,24(3):619-634
Microwave heating allows for the high-yield, one-step synthesis of the known triosmium complexes Os3(μ-Br)2(CO)10 (1), Os3(μ-I)2(CO)10 (2), and Os3(μ-H)(μ-OR)(CO)10 with R = methyl (3), ethyl (4), isopropyl (5), n-butyl (6), and phenyl (7). In addition, the new clusters Os3(μ-H)(μ-OR)(CO)10 with R = n-propyl (8), sec-butyl (9), isobutyl (10), and tert-butyl (11) are synthesized in a microwave reactor. The preparation of these complexes is easily accomplished without the need to first prepare an activated derivative of Os3(CO)12, and without the need to exclude air from the reaction vessel. The syntheses of complexes 1 and 2 are carried out in less than 15 min by heating stoichiometric mixtures of Os3(CO)12 and the appropriate halogen in cyclohexane. Clusters 3–6 and 8–10 are prepared by the microwave irradiation of Os3(CO)12 in neat alcohols, while clusters 7 and 11 are prepared from mixtures of Os3(CO)12, alcohol and 1,2-dichlorobenzene. Structural characterization of clusters 2, 4, and 5 was carried out by X-ray crystallographic analysis. High resolution X-ray crystal structures of two other oxidative addition products, Os3(CO)12I2 (12) and Os3(μ-H)(μ-O2CC6H5)(CO)10 (13), are also presented. 相似文献
318.
We report the large-scale synthesis of 1,3-cyclooctanedione in five steps with 29% yield. This molecule is a synthetic precursor to difluorinated cyclooctyne, which participates in a bioorthogonal copper-free click reaction with azides. The final step demonstrates the first successful application of the Wacker-Tsuji oxidation to form a cyclic 1,3-dione. 相似文献