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31.
Yasuda M Nakajima H Takeda R Yoshioka S Yamasaki S Chiba K Baba A 《Chemistry (Weinheim an der Bergstrasse, Germany)》2011,17(14):3856-3867
Boron complexes that contain new tridentate ligands, tris(o‐oxyaryl)methanes and ‐silanes, were prepared. These complexes had a cage‐shaped structure around a boron center and showed higher Lewis acidity and catalytic activity than open‐shaped boron compounds. The cage‐shaped ligands determined the properties of the borates by altering the geometry and were consistently bound to the metal center by chelation. The synthesized compounds were L?B(OC6H4)3CH, L?B(OC6H4)3SiMe, and its derivatives (L=THF or pyridine as an external ligand). Theoretical calculations suggested that the cage‐shaped borates had a large dihedral angle (Cipso‐O‐B‐O) compared with open‐shaped borates. The geometric effect due to the dihedral angle means that compared with open‐shaped, the cage‐shaped borates have a greater Lewis acidity. The introduction of electron‐withdrawing groups on the aryl moieties in the cage‐shaped framework increased the Lewis acidity. Substitution of a bridgehead Si for a bridgehead C decreased the Lewis acidity of the boron complexes because the large silicon atom reduces the dihedral angle of Cipso‐O‐B‐O. The ligand‐exchange rates of the para‐fluoro‐substituted compound B(OC6H3F)3CH and the ortho‐phenyl‐substituted compound B(OC6H3Ph)3CH were less than that of the unsubstituted borate B(OC6H4)3CH. The ligand‐exchange rate of B(OC6H4)3SiMe was much faster than that of B(OC6H4)3CH. A hetero Diels–Alder reaction and Mukaiyama‐type aldol reactions were more effectively catalyzed by cage‐shaped borates than by the open‐shaped borate B(OPh)3 or by the strong Lewis acid BF3?OEt2. The cage‐shaped borates with the bulky substituents at the ortho‐positions selectively catalyzed the reaction with less sterically hindered substrates, while the unsubstituted borate showed no selectivity. 相似文献
32.
Amaya T Hifumi M Okada M Shimizu Y Moriuchi T Segawa K Ando Y Hirao T 《The Journal of organic chemistry》2011,76(19):8049-8052
Oxosumanenes were synthesized through benzylic oxidation. The electronic and redox properties were revealed to exhibit the expanded π-conjugation compared to sumanene. Single-crystal X-ray analysis of monooxosumanene showed columnar π-stacking in a concave-convex fashion. Stereoselective trimethylation of the trioxo derivative was performed via 1,2-addition to the carbonyl groups. 相似文献
33.
Ko-Ki Kunimoto Kouji Kimura Takatomo Takai Hitoshi Senda Motoo Shiro Akio Kuwae 《光谱学快报》2013,46(4):509-522
Two polymorphic forms (I and II) of 4-fluorophenylpyruvic acid (F-PPA) were obtained by crystallization from different solvents, showing a melting point at 163.2 and 171.0 °C. Crystal structures of polymorphs I and II were determined by X-ray crystallography. IR and Raman spectra of the two polymorphs were measured and the spectral characteristics were compared with those of phenylpyruvic acid. the two polymorphs show similar molecular and crystal structures to each other, except for the molecular geometries of the enol and the carboxylic acid moieties. Distinct IR spectral differences which result from the crystal field splitting were observed between the two polymorphs. 相似文献
34.
A surface preparation method with fine SiO2 particles in water is developed to flatten Si(0 0 1) surfaces on the nanometer scale. The flattening performance of Si(0 0 1) surfaces after the surface preparation method is investigated by scanning tunneling microscopy. The observed surface is so flat that 95% of the view area (100 × 100 nm2) is composed of only three atomic layers, namely, one dominant layer occupying 50% of the entire area and two adjacent layers. Furthermore, a magnified image shows the outermost Si atoms regularly distributed along the 〈1 1 0〉 direction on terraces. 相似文献
35.
The optically active (R)- and (S)-flavanones were prepared by an enzymatically enantioselective hydrolysis of (±)-flavanone oxime O-acylates employing lipases, followed by hydrolysis with acid. 相似文献
36.
Osamu Yamashita Kouji Satou Hirotaka Odahara Shoichi Tomiyoshi 《Journal of Physics and Chemistry of Solids》2005,66(7):1287-1293
The p-type (Bi0.25Sb0.75)2Te3 doped with 3-12 wt% excess Te alone and n-type Bi2(Te0.94Se0.06)3 codoped with 0.017-0.026 wt% Te and 0.068-0.102 wt% I were prepared by the Bridgman method, to produce intentionally polycrystalline. Some of the as-grown specimens were annealed, in order to prepare specimens with much different ρ. These polycrystalline specimens have almost the same degree of alignment of the c plane parallel to the freezing direction. The electrical rersistivity ρ and thermal conductivity κ were measured at 298 K along the freezing direction and κ was plotted as a function of ρ. As a result, the lattice components κph obtained by subtracting the electronic component κel from the observed κ were found to decrease almost linearly with a decrease of ρ in both p- and n-type specimens, where κel was calculated using Wiedemann-Franz law. This tendency is consistent with the conventional result that κph becomes negligible small in metals. The significant decrease in κph with decrease in ρ is considered to be caused predominantly by the phonon scattering due to dopants. The relationship between κph and ρ was first clarified in the intermediate region between the metal and insulator. 相似文献
37.
This Letter theoretically discusses quasiparticle states and nuclear spin relaxation rates T1-1 in the quasi-one-dimensional superconductor (TMTSF)2PF6 under a magnetic field applied parallel to the conduction chains. We study the effects of Josephson-type vortices on T1(-1) by solving the Bogoliubov-de Gennes equation for p-, d- or f-wave pairing interactions. In the presence of line nodes in pairing functions, T1(-1) is proportional to T in sufficiently low temperatures because quasiparticles induced by vortices at the Fermi energy relax spins. We also try to identify the pairing symmetry of (TMTSF)2PF6. 相似文献
38.
39.
Kouji Hashimoto Kenta Kobayashi Mitsuhiro T. Nakao 《Numerical Functional Analysis & Optimization》2013,34(4-5):523-542
We propose two methods to enclose the solution of an ordinary free boundary problem. The problem is reformulated as a nonlinear boundary value problem on a fixed interval including an unknown parameter. By appropriately setting a functional space that depends on the finite element approximation, the solution is represented as a fixed point of a compact map. Then, by using the finite element projection with constructive error estimates, a Newton-type verification procedure is derived. In addition, numerical examples confirming the effectiveness of current methods are given. 相似文献
40.
Boron complexes surrounded with organic cages were controlled precisely by a remote atom placed at the bottom of the cage. A replacement of the bottom tether atom (carbon or silicon) changed the characteristics (kinetic and thermodynamic factors) of boron complexes by geometric effects. A theoretical study shows that the bottom atoms also control eigenvalues of MO. This cage complex will provide a systematic template for fine-tuning of metal complexes to create various properties. 相似文献