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131.
The thermally stable solids Re2(CO)8[μ-InRe(CO)5]2 and Re4(CO)12[μ3-InRe(CO)5]4 could be obtained by treatment of In with Re2(CO)10 in a bomb tube. A mechanism of the formation of the latter cluster from the first one is proposed. Compared with Re2(CO)8[μ-InRe(CO)5]2, Re4(CO)12[μ3_InRe(CO)5]4 shows in polar solvents an unusual high stability, which can be explained by the higher coordination number of In with rhenium carbonyl ligands. Re4(CO)12-[μ3-InRe(CO)5]4 dissolves monomerically in acetone, where as Re2(CO)8[μ-InRe(CO)5]2 dissociates yielding Re(CO)5? anions. Single-crystal X-ray analyses of Re4(CO)12[μ3-InRe(CO)5]4 establish the metal skeleton. The central molecular fragment Re4(CO)12 contains a tetrahedral arrangement of four bonded Re atoms [ReRe 302.8 (5) pm]. The triangles of this fragment are capped with a μ3-InRe(CO)5 group each [InRe(terminal) 273.5 (7) pm; InRe (polyhedral) 281.8 (7) pm]. The bridging type of In atoms with the Re4 tetrahedron and the metal skeleton was realized for the first time. By treating Re4(CO)12[μ3-InRe(CO)5]4 with Br2 the existence of Re(CO)5 ligands could be proved by isolating BrRe(CO)5. 相似文献
132.
A reduced surface electric field in AlGaN/GaN high electron mobility transistor (HEMT) is investigated by employing a localized Mg-doped layer under the two-dimensional electron gas (2-DEG) channel as an electric field shaping layer. The electric field strength around the gate edge is effectively relieved and the surface electric field is distributed evenly as compared with those of HEMTs with conventional source-connected field plate and double field plate structures with the same device physical dimensions. Compared with the HEMTs with conventional source-connected field plate and double field plate, the HEMT with Mg-doped layer also shows that the breakdown location shifts from the surface of the gate edge to the bulk Mg-doped layer edge. By optimizing both the length of Mg-doped layer, Lm, and the doping concentration, a 5.5 times and 3 times the reduction in the peak electric field near the drain side gate edge is observed as compared with those of the HEMTs with source-connected field plate structure and double field plate structure, respectively. In a device with VGS=-5 V, Lm=1.5 μm, a peak Mg doping concentration of 8× 1017 cm-3 and a drift region length of 10 μm, the breakdown voltage is observed to increase from 560 V in a conventional device without field plate structure to over 900 V without any area overhead penalty. 相似文献
133.
Quiver Hopf algebras 总被引:1,自引:0,他引:1
In this paper we study subHopfalgebras of graded Hopf algebra structures on a path coalgebra kQc. We prove that a Hopf structure on some subHopfquivers can be lifted to a Hopf structure on the whole Hopf quiver. If Q is a Schurian Hopf quiver, then we classified all simple-pointed subHopfalgebras of a graded Hopf structure on kQc. We also prove a dual Gabriel theorem for pointed Hopf algebras. 相似文献
134.
Valentin Deaconu Fred Shultz 《Transactions of the American Mathematical Society》2007,359(4):1889-1924
For each piecewise monotonic map of , we associate a pair of C*-algebras and and calculate their K-groups. The algebra is an AI-algebra. We characterize when and are simple. In those cases, has a unique trace, and is purely infinite with a unique KMS state. In the case that is Markov, these algebras include the Cuntz-Krieger algebras , and the associated AF-algebras . Other examples for which the K-groups are computed include tent maps, quadratic maps, multimodal maps, interval exchange maps, and -transformations. For the case of interval exchange maps and of -transformations, the C*-algebra coincides with the algebras defined by Putnam and Katayama-Matsumoto-Watatani, respectively.
135.
In solution, the [(tim)Co](2+) complex (tim = 2,3,9,10-tetramethyl-1,4,8,11-tetraazacyclotetradeca-1,3,8,10-tetraene) reacts only slowly with O(2), but upon adsorption on graphite electrodes, it becomes an active catalyst for the reduction of O(2) to H(2)O(2). The electroreduction of O(2) proceeds in a single voltammetric step at close to the diffusion-controlled rate at a relatively positive potential (0.25 V vs SCE). The remarkable enhancement in catalytic activity is attributed to a higher affinity for O(2) of the adsorbed complex as a result of its interactions with functional groups on the surface of roughened or oxidized graphite. A possible mechanism for the catalytic reduction of O(2) is proposed. It differs from the one employed by the analogous [(hmc)Co](2+) complex (hmc = C-meso-5,7,7,12,14,14-hexamethyl-1,4,8,11-tetraazacyclotetradecane) which operates at less positive potentials and exhibits two separated voltammetric steps in the reduction of O(2), via [(hmc)CoOOH](2+), to H(2)O(2). 相似文献
136.
Cyclodimerization versus Polymerization of Methyl Methacrylate Induced by N‐Heterocyclic Carbenes: A Combined Experimental and Theoretical Study 下载免费PDF全文
Winnie Nzahou Ottou Damien Bourichon Dr. Joan Vignolle Anne‐Laure Wirotius Dr. Fredéric Robert Prof. Yannick Landais Dr. Jean‐Marc Sotiropoulos Dr. Karinne Miqueu Prof. Daniel Taton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2014,20(14):3989-3997
The activation behavior of two N‐heterocyclic carbenes (NHCs), namely, 1,3‐bis(isopropyl)imidazol‐2‐ylidene(NHCiPr) and 1,3‐bis(tert‐butyl) imidazol‐2‐ylidene (NHCtBu), as organic nucleophiles in the reaction with methyl methacrylate (MMA) is described. NHCtBu allows the polymerization of MMA in DMF at room temperature and in toluene at 50 °C, whereas NHCiPr reacts with two molecules of MMA, forming an unprecedented imidazolium–enolate cyclodimer (NHCiPr/MMA=1:2). It is proposed that the reaction mechanism occurs by initial 1,4‐nucleophilic addition of NHCiPr to MMA, generating a zwitterionic enolate 2 , followed by addition of 2 to a second MMA molecule, forming a linear imidazolium–enolate 3 (NHCiPr/MMA=1:2). Proton transfer, generating intermediate 5 , followed by cyclization and release of methanol yielded the aforementioned zwitterionic cyclodimer 1:2 adduct 7 , the molecular structure of which has been established by NMR spectroscopy, X‐ray diffraction, and mass spectrometry. This unexpected difference between NHCtBu and NHCiPr in the reaction with MMA (polymerization and cyclodimerization, respectively) can be rationalized by using DFT calculations. In particular, the nature of the NHC strongly influences the cyclodimerization pathway, the cyclization of 5 and the release of methanol are the discriminating step and limiting step, respectively. In the case of NHCtBu, both steps are strongly disfavoured compared with that of NHCiPr (energetic difference of around 14 and 9 kcal mol?1, respectively), preventing the cyclization mechanism from a kinetic viewpoint. Moreover, addition of a third molecule of MMA in the polymerization pathway results in a lower activation barrier than that of the limiting step in the cyclodimerization pathway (difference of around 14 kcal mol?1), in agreement with the formation of polymethyl methacrylate (PMMA) by using NHCtBu as nucleophile. 相似文献
137.
From the N‐Heterocyclic Carbene‐Catalyzed Conjugate Addition of Alcohols to the Controlled Polymerization of (Meth)acrylates 下载免费PDF全文
Winnie Nzahou Ottou Damien Bourichon Dr. Joan Vignolle Anne‐Laure Wirotius Dr. Fredéric Robert Prof. Yannick Landais Dr. Jean‐Marc Sotiropoulos Dr. Karinne Miqueu Prof. Daniel Taton 《Chemistry (Weinheim an der Bergstrasse, Germany)》2015,21(26):9447-9453
Among various N‐heterocyclic carbenes (NHCs) tested, only 1,3‐bis(tert‐butyl)imidazol‐2‐ylidene (NHCtBu) proved to selectively promote the catalytic conjugate addition of alcohols onto (meth)acrylate substrates. This rather rare example of NHC‐catalyzed 1,4‐addition of alcohols was investigated as a simple means to trigger the polymerization of both methyl methacrylate and methyl acrylate (MMA and MA, respectively). Well‐defined α‐alkoxy poly(methyl (meth)acrylate) (PM(M)A) chains, the molar masses of which could be controlled by the initial [(meth)acrylate]0/[ROH]0 molar ratio, were ultimately obtained in N,N‐dimethylformamide at 25 °C. A hydroxyl‐terminated poly(ethylene oxide) (PEO‐OH) macro‐initiator was also employed to directly access PEO‐b‐PMMA amphiphilic block copolymers. Investigations into the reaction mechanism by DFT calculations revealed the occurrence of two competitive concerted pathways, involving either the activation of the alcohol or that of the monomer by NHCtBu. 相似文献
138.
Precision capacitance dilatometry provides a sensitive measure of the thermal strain developed in a sample undergoing a structural distortion with its varying temperature. The A15 structure compounds, V3Si and Nb3Sn, are well known to undergo distortion from their cubic structures at room temperature to tetragonal structures (c/a > 1 for V3Si and c/a < 1 for Nb3Sn) at low temperatures. In the past, highly anomalous thermal expansion behaviour recorded for these materials has been attributed to a strongly anharmonic lattice potential manifesting itself in unusually high, and strongly temperature-dependent, Grüneisen parameters. Further studies on polycrystalline material revealed this anomalous expansion to be highly anisotropic at temperatures for which, according to conventional diffraction data, the materials are cubic. This behaviour was linked to control of sample morphology by a residual stress field resulting from sample preparation. More recent experiments, in which the transformation morphology has been controlled by the application of external stresses to single crystal V3Si and polycrystalline samples of Nb3Sn and Nb3(Sn1-x Sb x ), have confirmed the occurrence of significant anisotropy in the thermal strain in the cubic phase, well above the structural transformation. We link this departure from cubic symmetry with the well-known soft-mode character of these materials and the associated “central peak” scattering which is also observed well above the transformation temperature. We are led to propose that the “central peak” is the precursor to a Bragg reflection for the transformation structure. This coincidence between “central peak” scattering and the reciprocal lattice for the transformed phase in Ti-Ni has been termed a “ghost lattice”. 相似文献
139.
Fred L. Tobiason Duane D. Swank Gérard Vergoten Pierre Legrand 《Journal of carbohydrate chemistry》2013,32(7):959-974
ABSTRACT The flexible ring structures of α- and β-D-idopyranose have been investigated by conformational analysis using structures generated by MacroModel and GMMX search protocols. The lowest energy structures found during the conformer search for the 4 C 1, 1 C 4, O S 2 and the 3 S 1 structures were then examined by AM1 and Gaussian ab initio methods at the HF/6-311G** and HF/6-31+G* levels. The B 2,5 conformer found for β-D-idopyranose at 14 kJ/mol by GMMX and 29.5 kJ/mol for α-D-idopyranose by MacroModel would not contribute to Boltzmann-averaged 1H NMR coupling constants. The Merck MMFF force field tends to overweight the 1 C 4 structures, making these the lowest energy conformers for both anomers. Boltzmann-averaged coupling constants are heavily weighted by this structure in the MMFF search conformer ensemble. Averaged proton coupling constants determined using MMFF fit very well for α-D-idopyranose compared to the observed values, but fit poorly for the β-anomer. Ab initio results place the 1 C 4 conformer at lowest energy for the α-anomer and place the 4 C 1 conformer at lowest energy for the β-anomer. The GMMX and MM3* force fields find the 4 C 1 conformer to have the lowest energies for both anomers. 相似文献
140.