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11.
Pavel Smirnov Hisanobu Wakita Masaharu Nomura Toshio Yamaguchi 《Journal of solution chemistry》2004,33(6-7):903-922
The structure and complex formation of concentrated aqueous gallium(III) bromide (GaBr3) solutions have been investigated over a temperature range 80–333 K by Raman spectroscopy, X-ray absorption fine structure (XAFS), and X-ray diffraction. The Raman spectra obtained at various [Br?]/[Ga3+] molar ratios and temperatures have shown that complex formation between Ga3+ and Br? occurs as a predominant species, with [GaBr4]? at [Ga3+] as high as 1~2 M (M = mol?dm ?3) and [Br?]/[Ga3+] ratios > ~2, and that cooling of the solutions favors the formation of the aqua Ga3+. The intermediate species were not seen in the Raman spectra. The XAFS data have revealed that the aqua complex has a sixfold coordination as [Ga(H2O)6]3+ with a Ga3+–H2O distance of (1.96 ± 0.02) Å, whereas the [GaBr4]? complex has a Ga3+–Br? distance of (2.33± 0.02) Å, and that vitrification of the aqueous GaBr3 solution at liquid nitrogen temperature shifts the equilibrium toward the aqua complex. The X-ray diffraction data at different subzero temperatures have shown a tendency of decreasing Ga3+–Br? and increasing Ga3+–H2O interactions with lowering temperature, confirming the preference of aqua Ga3+ in the supercooled liquid state as well as in the glassy state. The Ga3+–H2O distance of ~1.8 Å for the tetrahedral coordination was found in a 2.01 M gallium(III) bromide solution with a [Br?]/[Ga3+] ratio of 3.7 and gradually increased to a value of 1.92 Å for octahedral geometry with decreasing temperature, suggesting that equilibrium shifts from [GaBr4]? to [Ga(H2O)6]3+ through intermediate species, [GaBr n ](3?n)+ (n = 2 and 3). The Ga3+–Br? and Br?–Br? distances within [GaBr4]? with an almost tetrahedral symmetry are (2.35± 0.02) and (3.82± 0.03) Å, respectively. The Ga3+ has the second hydration shell at (4.03± 0.03) Å and the hydration of Br? is characterized with a Br?–H2O distance of (3.35± 0.02) Å at all temperatures investigated. 相似文献
12.
Hiroyuki Ishibashi Motofumi Okada Atsuko Akiyama Kazuyuki Nomura Masazumi Ikeda 《Journal of heterocyclic chemistry》1986,23(4):1163-1166
2,3-Dihydro-5H-1,4-benzoxathiepins were prepared by intramolecular Friedel-Crafts reactions of ethyl α-[2-(aryloxy)ethylthio]-α-chloroacetates or by acid-catalyzed cyclizations of ethyl α-[2-(aryloxy)ethylsulfinyl]-acetate. 1,2,3,5-Tetrahydro-4,1-benzothiazepines were similarly prepared. 相似文献
13.
Stereoselective polymerization of racemic lactide (rac-LA) was examined using Al-achiral ligand complexes. By introduction of substituents in aromatic rings of Schiff base ligands, a higher selectivity was obtained without any chiral auxiliaries in the catalyst via a chain-end control mechanism. The T(m) values (T(m) 170-192 degrees C) were comparable to or higher than that of homochiral polymer, poly(L-LA) (T(m) 162 degrees C), and a thermally more stable polylactide than poly(L-LA) was prepared from rac-LA. 相似文献
14.
K. Nomura H. Reuther E. Richter Y. Ujihira 《Journal of Radioanalytical and Nuclear Chemistry》1995,190(2):299-313
Changes in the magnetic structure of Fe–Si–Al films due to Al and N ion implantation were studied by57Fe Conversion Electron Mössbauer Spectrometry (CEMS). The peaks of the magnetic sextets due to the crystalline films became broader by implantation with 5×1016 Al/cm2, suggesting the formation of amorphous phases. In the CEM spectrum of one sample with large grains implanted with 1×1017 Al/cm2 a crystalline -Fe phase appeared. N implantation with the same dose did not amorphize the sample but the components with high magnetic hyperfine fields were enhanced. 相似文献
15.
K. Nomura 《Graphs and Combinatorics》1995,11(2):139-140
Let be a bipartite distance-regular graph of even valencyk. Let us consider the intersection array modulo 2, which would become Lett be the length of any series of (1, 0, 1)'s witht > 1. Thent + 1|r
1 + 1, withr
1 the length of the first series. 相似文献
16.
Takaaki Nomura 《Annals of Global Analysis and Geometry》1994,12(1):237-260
We study the set of rankp idempotents in a topologically simple Hilbert Jordan algebra (JH-algebra for short). To produce the differential geometric structure on, we establish Jordan algebraic results concerning the structure of some two-generator subalgebras. We identify geodesics, the Riemannian distance and the sectional curvature of by using the Jordan algebraic structure. 相似文献
17.
In a previous paper we studied the Young's and shear modulus of a high-angle twist grain boundary (5) in Cu, using the EAM, and related it to the uniaxial strain derivatives of single crystals. In this paper, we discuss elastic properties of ten additional twist grain boundaries, from 8.8–43.6°. The monolayer Young's modulus at each boundary was calculated and found to be 20–50% higher than the bulk value for all eleven boundaries for both csl and type1 structures. The monolayer shear modulus at each boundary was calculated and found to be 93–98% lower than the bulk value for six grain boundaries with csl structure and found to decrease with increasing twist angle. The critical shear stress was also calculated for eleven boundaries with csl structure and found to roughly decrease with increasing twist angle. 相似文献
18.
Akito Nomura 《manuscripta mathematica》1993,79(1):379-390
LetL/k be a finite Galois extension with Galois groupG, and
a group extension. We study the existence of the Galois extensionM/L/k such that the canonical projection Gal(M/k)→Gal(L/k) coincides with the given homomorphismj:E→G and thatM/L is unramified. 相似文献
19.
Phenols are deprotected with weak bases from their tert-butoxycarbonyl (Boc) derivatives. Boc deprotection with bases can avoid side reactions during the deprotection with acids. We note the lability of the Boc to bases and are able to utilize it as a new cleavage condition for synthetic studies. 相似文献
20.
Yotaro Morishima Shigeki Nomura Mikiharu Kamachi 《Journal of polymer science. Part A, Polymer chemistry》1994,32(16):3141-3146
3,7-Diethyl- 10-phenylphenothiazine (DEPPT), a phenothiazine derivative whose 3,7- and 10-positions are blocked, was synthesized. Potentiostatic electrolysis of DEPPT in acetonitrile (ACN) in the presence of 0.1M of LiClO4 at 0.7 V (vs. Ag/Ag/Cl) yielded the stable cation radical of DEPPT (DEPPT+·) which was characterized by cyclic voltammetry, UV-visible spectroscopy, and ESR spectrometry. Stable cation radicals of 10-phenylphenothiazine and 3,7-diethyl-10-methylphenothiazine were also prepared. The cationic polymerization of n-butyl vinyl ether was initiated by these cation radicals, including DEPPT·+. The electron transfer mechanism for the initiation step, which we proposed previously, was supported by the fact that DEPPT·+ was capable of initiating the polymerization; dimerization of DEPPT·+ by releasing protons is precluded because 3,7- and 10-positions are all blocked. © 1994 John Wiley & Sons, Inc. 相似文献