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排序方式: 共有261条查询结果,搜索用时 15 毫秒
51.
Prof. Takayuki Nakajima Mizuki Takubo Yurika Komura Yuki Maeda Miwa Sato Maki Zouda Prof. Tomoaki Tanase 《欧洲无机化学杂志》2023,26(9):e202200648
A new series of cationic heterodinuclear complexes, [M1M2Cl2(meso-dpmppp)(RNC)2]PF6 (M1=Ni, M2=Rh, R=tBu ( 1 a ); M1=Pd, M2=Rh, R=tBu ( 2 a ), Xyl ( 2 b ); M1=Pt, M2=Rh, R=tBu ( 3 a ), Xyl ( 3 b ); M1=Pd, M2=Ir, R=tBu ( 4 a )), supported by a tetradentate phosphine ligand, meso-Ph2PCH2P(Ph)(CH2)3P(Ph)CH2PPh2 (meso-dpmppp), were synthesized by stepwise reactions of meso-dpmppp with NiCl2 ⋅ 6H2O or MCl2(cod) (M=Pd, Pt), forming mononuclear metalloligands of [M1Cl2(meso-dpmppp)], and with [M2Cl(cod)]2 (M2=Rh, Ir) and RNC (R=tBu, Xyl) in the presence of [NH4][PF6]. The related neutral PdRh complex, [PdRhCl3(meso-dpmppp)(XylNC)] ( 5 ), was also prepared. The structures of 1 – 5 were determined by X-ray analyses to contain two square planar d8 metal centers with face-to-face arrangement, where meso-dpmppp supports M1 and M2 metal ions in cis/trans-P,P coordination mode, combining cis-{M1P2Cl2} and trans-{M2P2(CNR)2} units. Complexes 1 – 4 showed an intence characteristic absorption around 422–464 nm derived from RhI→RNC MLCT transition (HOMO→LUMO+1), which are influenced by changing M1 (NiII, PdII, PtII) metal ions since HOMO composed of dσ* orbitals appreciably destabilized by changing M1 from Ni to Pd, and Pt. The electronic structures of 1 a – 4 a were investigated on the basis of DFT calculations and NBO analyses to show weak but noticeable d8–d8 metallophilic interaction as empirical dispersion energy of 0.9–1.5 kcal/mol without M1–M2 covalent bonding interaction. In addition, 1 – 5 were utilized as catalysts for hydrosilylation of styrene, and the NiRh complex 1 a was found to show higher activity and chemo- and regioselectivity compared with 2 – 5 . 相似文献
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54.
New mononuclear compounds of the ligand 1-(2-hydroxyphenyl)-3-phenylpropane-1,3-dione (H2L) with Cu(II) and several lanthanoid(III) ions, where Ln(III) = Pr, Nd, Eu, Gd, have been synthesized and characterized by spectroscopic methods and X-ray crystal structure determinations. In all compounds, the ligand coordinates in a bidentate chelating manner, using the diketone function. In the [Cu(HL)2], the coordination geometry of Cu(II) ion is slightly distorted square-planar; two strong intramolecular (OH?O) hydrogen-bonding interactions are established between the phenolate group and the neighboring ketone function. The lanthanoid(III) compounds have the general formula [Ln(HL)3(CH3OH)2] · CH3OH · 2H2O; the lanthanoid(III) ion (Ln) is eight-coordinated and the coordination geometry is based on a distorted square-antiprism. In addition to the intramolecular hydrogen bonding (OH?O), intermolecular hydrogen-bonding interactions are also present between the coordinated methanol molecule and the non-coordinated methanol molecule giving rise to a three-dimensional network. 相似文献
55.
M Viciano-Chumillas M Giménez-Marqués S Tanase I Mutikainen U Turpeinen JM Smits R de Gelder L Jos de Jongh J Reedijk 《Dalton transactions (Cambridge, England : 2003)》2012,41(34):10249-10257
New manganese compounds [Mn(HphpzMe)(2)(H(2)phpzMe)(HCO(2))] (1), [Mn(2)(phpzMe)(2)(HphpzMe)(2)(OCH(3))]·2CH(3)OH (2), Na{[Mn(HphpzPh)(phpzPh)(MeOH)(2)](2)}(HCO(2)) (3), [Mn(HphpzPh)(2)(EtOH)(2)]ClO(4)·2EtOH (4) and [Mn(HphpzPh)(2)N(3)] (5) were synthesized and characterized with various techniques. 1, 4 and 5 are mononuclear manganese(iii) compounds, 2 is a mixed-valence dinuclear manganese(iii/iv) compound, and 3 is a trinuclear compound containing two manganese(iii) ions and a sodium(i) ion. A remarkable feature is the spontaneous formation of the formate ion as a result of the methanol or methoxide oxidation in compounds 1 and 3. Using ethanol precludes the formation of the formate and compound 4 is obtained. The molecular structure of all compounds is stabilized by supramolecular interactions, including strong hydrogen bonding and π-π interactions. 相似文献
56.
Takeya H Miyazawa K Kato R Wakahara T Ozaki T Okazaki H Yamaguchi T Takano Y 《Molecules (Basel, Switzerland)》2012,17(5):4851-4859
We synthesized superconducting fullerene nanowhiskers (C(60)NWs) by potassium (K) intercalation. They showed large superconducting volume fractions, as high as 80%. The superconducting transition temperature at 17 K was independent of the K content (x) in the range between 1.6 and 6.0 in K-doped C(60) nanowhiskers (K(x)C(60)NWs), while the superconducting volume fractions changed with x. The highest shielding fraction of a full shielding volume was observed in the material of K(3.3)C(60)NW by heating at 200 °C. On the other hand, that of a K-doped fullerene (K-C(60)) crystal was less than 1%. We report the superconducting behaviors of our newly synthesized K(x)C(60)NWs in comparison to those of K(x)C(60) crystals, which show superconductivity at 19 K in K(3)C(60). The lattice structures are also discussed, based on the x-ray diffraction (XRD) analyses. 相似文献
57.
Yahia Didane Rocio Ponce Ortiz Jian Zhang Keijyu Aosawa Toshinori Tanisawa Hecham Aboubakr Frédéric Fages Jörg Ackermann Noriyuki Yoshimoto Hugues Brisset Christine Videlot-Ackermann 《Tetrahedron》2012,68(24):4664-4671
Solution and solid-state properties of two new perfluoroalkyl end-substituted analogues of distyryl-bithiophene (CF3-DS2T and diCF3-DS2T) are presented. Vacuum deposited thin films were investigated by atomic force microscopy, X-ray diffraction, and implemented as active layers into organic thin film transistors. While physicochemical measurements in solution suggest a preferential hole injection and transport inside CF3-DS2T and diCF3-DS2T films, electrical measurements performed under high vacuum show that CF3-DS2T behaves as n-type semiconductor while no charge transport was measured in diCF3-DS2T. The results highlighted the importance of substituents on conjugated backbone and on the resulting fine ordering in solid state to control the charge transport. 相似文献
58.
Near-well effects can have a strong impact on many subsurface flow processes. In oil production, because dissolved gas is
released from the oil phase when the pressure falls below the bubble point, the detailed pressure field in the immediate vicinity
of a production well strongly impacts gas (and thus oil) production. This effect is complicated by the interplay of fine-scale
heterogeneity and two-phase flow physics, and can be difficult to capture in coarse-grid simulations. In this article, we
develop and apply a new upscaling (coarse-graining) procedure to capture such near-well subgrid effects in coarse-scale flow
simulation models. The method entails the use of preprocessing computations over near-well domains [referred to as local well
models (LWM)] for the determination of upscaled single-phase and two-phase near-well parameters. These parameters are computed
by minimizing the mismatch between fine and coarse-scale flows over the LWM. Minimization is accomplished using a gradient-based
optimization procedure, with gradients calculated through solution of adjoint equations. The boundary conditions applied on
the LWM can impact the upscaled parameters, but these boundary conditions depend on the global flow and are not, therefore,
known a priori. In order to circumvent this difficulty, an adaptive local–global procedure is applied. This entails performing
a global coarse-scale simulation with initial estimates for well-block parameters. The resulting pressure and saturation fields
are then used to define local boundary conditions for the near-well computations. The overall procedure is applied to several
example problems and is shown to provide results in close agreement with reference fine-scale computations. Significant improvement
in accuracy over existing near-well upscaling treatments is demonstrated, particularly for a heavy oil case with oil viscosity
of ~104 cp. 相似文献
59.
Maria Carmelita Z. Kasuya Maki Ikeda Kazuhiko Hashimoto Toshinori Sato 《Journal of carbohydrate chemistry》2013,32(7):705-715
The synthesis of sialylated glycosides using saccharide primers and cells was investigated. α · and β · Saccharide primers were chemically synthesized and introduced into B16 melanoma cells to prime oligosaccharide synthesis. Incorporation of α‐ and β‐dodecyl lactosides into B16 cells resulted in the sialylation of the galactose residue to give GM3‐type oligosaccharides. The β‐dodecyl galactoside primer was sialylated but the α‐dodecyl galactoside primer was not. Both the α‐ and β‐dodecyl glucoside primers were not elongated. In the glycosylation of primers by cells, this research confirmed that sialyl transferases tolerate acceptor modifications and are permissive to primer elongation regardless of the α‐ or β‐linkage to the aglycon unit. However, the presence of the terminal galactose residue that is β‐linked to the adjacent saccharide or aglycon unit is essential for sialylation by cellular enzymes to occur. 相似文献
60.
Nabajyoti Saikia Shigeru Kato Toshinori Kojima 《Journal of Thermal Analysis and Calorimetry》2012,109(1):273-286
Tricalcium aluminate (Ca3Al2O6, C3A) containing 0?C5% of Sn was synthesized by solid-state method, and the products were characterized by XRD technique. Differential thermo-analytical technique (DTA) along with X-ray diffraction (XRD) analysis and scanning electron microscopy (SEM) were applied to study the hydration behaviour of different C3A samples with and without the presence of gypsum. Results indicate that C3A can accommodate small amount of Sn in its structure and remaining amount forms SnO2. Hydration studies of the synthesized C3A shows that the additions of 0.5 and 1% Sn increase and 2% Sn decrease the reactivity of C3A at the initial period (<3?h) of hydration. Increasing additions of Sn also increase the amounts of amorphous phases and hexagonal calcium aluminate hydrates in the cement pastes. The stabilities of these hydration products also increase with increasing content of Sn in C3A at the experimental conditions. The presence of Sn significantly changes the hydration of C3A and gypsum solid mixture at the initial period of hydration by enhancing the formation of more amounts of AFt and AFm phases. However, at the later stage of hydration (on or after 3?days), the hydration products in C3A and gypsum pastes with and without the presence of Sn are almost similar. 相似文献