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1.
    
The reaction of [{(η5-C5Me5)M(μ-Cl)Cl}2] {where M = Rh (1), Ir (2)} with functionalized phosphine viz., diphenyl-2-pyridylphosphine (PPh2Py) in dichloromethane solvent yield neutral ϰ1-P-coordinated rhodium and iridium complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3 and [(η5-C5Me5) IrCl21-P-PPh2Py)]4. Reaction of complexes 1 and 2 with the ligand PPh2Py in methanol under reflux give bis-substituted complexes such as [(η5-C5Me5)RhCl(ϰ1-P-PPh2Py)2]+ 5 and [(η5-C5Me5)IrCl(ϰ1-P-PPh2Py)2]+ 6, whereas stirring in methanol at room temperature gives P-, N-chelating complexes of the type [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5)IrCl(ϰ2-P-N-PPh2Py)]+ 8. Neutral ϰ1-P-coordinated complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3 and [(η5-C5Me5)IrCl21-P-PPh2Py)]4 easily undergo conversion to the cationic P-, N-chelating complexes [(η5-C5Me5)RhCl(ϰ2-P-N-PPh2Py)]+ 7 and [(η5-C5Me5) IrCl(ϰ2-P, N-PPh2Py)]+ 8 on stirring in methanol at room temperature. These complexes are characterized by FT-IR and FT-NMR spectroscopy as well as analytical methods. The molecular structures of the representative complexes [(η5-C5Me5)RhCl21-P-PPh2Py)]3, [(η5-C5Me5)IrCl21-P-PPh2Py)]4 and hexafluorophosphate salt of complex [(η5-C5Me5)IrCl(ϰ2-P-PPh2Py)2]+ 6 are established by single-crystal X-ray diffraction methods  相似文献   
2.
Rhodium catalysts have been prepared on palygorskite and montmorillonite (clay) supports by reduction with hydrogen (1 atmosphere) at room temperature of a cationic organometallic rhodium compound anchored to the support. The activity of these catalysts for the hydrogenation of liquid-phase 1-hexene remains constant with increase of prehydrogenation time and with re-use for several runs. No rhodium leaching is observed.  相似文献   
3.
A graph G is N2locally connected if for every vertex ν in G, the edges not incident with ν but having at least one end adjacent to ν in G induce a connected graph. In 1990, Ryjá?ek conjectured that every 3‐connected N2‐locally connected claw‐free graph is Hamiltonian. This conjecture is proved in this note. © 2004 Wiley Periodicals, Inc. J Graph Theory 48: 142–146, 2005  相似文献   
4.
对求解非线性方程方法的探索   总被引:2,自引:0,他引:2  
BaiCL在2001年提出了双曲函数法,并把解设成具体的双曲函数,即sinhw和coshw的线性组合.本文把解设成是由2个函数f(ξ)和g(ξ)组成的线性组合,它们可以有多种取法,从而使方程更直接、更有效.借助数学软件Maple,用改进后的方法和吴文俊消元法,求解Bai C L文中的一个例子,获得了包含Bai文结果在内的更为丰富、精确的行波解.  相似文献   
5.
A tridentate ligand, BPIEP: 2,6‐bis[1‐(2,6‐diisopropyl phenylimino) ethyl] pyridine, having central pyridine unit and two peripheral imine coordination sites was effectively employed in controlled/“living” radical polymerization of MMA at 90°C in toluene as solvent, CuIBr as catalyst, and ethyl‐2‐bromoisobutyrate (EBiB) as initiator resulting in well‐defined polymers with polydispersities Mw/Mn ≤ 1.23. The rate of polymerization follows first‐order kinetics, kapp = 3.4 × 10?5 s?1, indicating the presence of low radical concentration ([P*] ≤ 10?8) throughout the reaction. The polymerization rate attains a maximum at a ligand‐to‐metal ratio of 2:1 in toluene at 90°C. The solvent concentration (v/v, with respect to monomer) has a significant effect on the polymerization kinetics. The polymerization is faster in polar solvents like, diphenylether, and anisole, as compared to toluene. Increasing the monomer concentration in toluene resulted in a better control of polymerization. The molecular weights (Mn,SEC) increased linearly with conversion and were found to be higher than predicted molecular (Mn,Cal). However, the polydispersity remained narrow, i.e., ≤1.23. The initiator efficiency at lower monomer concentration approaches a value of 0.7 in 110 min as compared to 0.5 in 330 min at higher monomer concentration. The aging of the copper salt complexed with BPIEP had a beneficial effect and resulted in polymers with narrow polydispersitities and higher conversion. PMMA obtained at room temperature in toluene (33%, v/v) gave PDI of 1.22 (Mn = 8500) in 48 h whereas, at 50°C the PDI is 1.18 (Mn = 10,300), which is achieved in 23 h. The plot of lnkapp versus 1/T gave an apparent activation energy of polymerization as (ΔEapp) 58.29 KJ/mol and enthalpy of equilibrium (ΔH0eq) to 28.8 KJ/mol. Reverse ATRP of MMA was successfully performed using AIBN in bulk as well as solution. The controlled nature of the polymerization reaction was established through kinetic studies and chain extension experiments. © 2005 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 43: 4996–5008, 2005  相似文献   
6.
Multicrystalline silicon was grown by unidirectional solidification method using the accelerated crucible rotation technique. The application of the accelerated crucible rotation technique in unidirectional solidification method induced growth striations across the axial direction of the grown crystal. This striation pattern was observed from carbon concentration distribution, obtained by using Fourier transform infrared spectroscopy. The generated striation pattern was found to be weak and discontinuous. Some striations were absent, probably due to back melting, caused during each crucible rotation. From the growth striations and applied time period in crucible rotation, the growth rate was estimated by using Fourier transformation analysis.  相似文献   
7.
To investigate the position and amount of the CF3 group affecting the coloration of polyimides (PIs), we prepared 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]hexafluoropropane ( 2 ) with four CF3 groups with 2‐chloro‐5‐nitrobenzotrifluoride and 2,2‐bis(4‐hydroxyphenol)hexafluoropropane. A series of soluble and light‐colored fluorinated PIs ( 5 ) were synthesized from 2 and various aromatic dianhydrides ( 3a – 3f ). 5a – 5f had inherent viscosities ranging from 0.80 to 1.19 dL/g and were soluble in amide polar solvents and even in less polar solvents. The glass‐transition temperatures of 5 were 221–265 °C, and the 10% weight‐loss temperatures were above 493 °C. Their films had cutoff wavelengths between 343 and 390 nm, b* values (a yellowness index) ranging from 5 to 41, dielectric constants of 2.68–3.01 (1 MHz), and moisture absorptions of 0.03–0.29 wt %. In a comparison of the PI series 6 – 8 based on 2,2‐bis[4‐(4‐aminophenoxy)phenyl]hexafluoropropane, 2,2‐bis[4‐(4‐amino‐2‐trifluoromethylphenoxy)phenyl]propane, and 2,2‐bis[4‐(4‐aminophenoxy)phenyl]propane, we found that the CF3 group close to the imide group was more effective in lowering the color; this means that CF3 of 5 , 7 , and 8f was more effective than that of 6c . The color intensity of the four PI series was lowered in the following order: 5 > 7 > 6 > 8 . The PI 5f , synthesized from diamine 2 and 4,4′‐hexafluoroisopropylidenediphthalic anhydride, had six CF3 groups in a repeated segment, so it exhibited the lightest color among the four series. © 2003 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem 41: 922–938, 2003  相似文献   
8.
The oxidation of symmetrical disulfides [D ,L ‐cystine ( 1 ) and 3,3′‐dithiobis(propionic acid) ( 2 )] with hydrogen peroxide in D2O–NaOH solution (pH 10–11) was studied by NMR spectroscopy. Assignments of the proton and carbon NMR signals of starting materials ( 1 and 2 ) and products of oxidation are based on conventional 1D NMR methods (DEPT, selective spin decoupling). Formation of C—S bond cleavage products or, in case of 2 , partially oxidized intermediates was not detected. The accelerating effect of Cu2+ cations, but not Fe3+ cations, on the oxidation rate of 1 in basic medium was demonstrated. Copyright © 2002 John Wiley & Sons, Ltd.  相似文献   
9.
This paper presents an evaluation of the capability of turbulence models available in the commercial CFD code FLUENT 6.0 for their application to hydrofoil turbulent boundary layer separation flow at high Reynolds numbers. Four widely applied two‐equation RANS turbulence models were assessed through comparison with experimental data at Reynolds numbers of 8.284×106 and 1.657×107. They were the standard k–εmodel, the realizable k–εmodel, the standard k–ωmodel and the shear‐stress‐transport (SST) k–ωmodel. It has found that the realizable k–εturbulence model used with enhanced wall functions and near‐wall modelling techniques, consistently provides superior performance in predicting the flow characteristics around the hydrofoil. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   
10.
A least‐squares meshfree method based on the first‐order velocity–pressure–vorticity formulation for two‐dimensional incompressible Navier–Stokes problem is presented. The convective term is linearized by successive substitution or Newton's method. The discretization of all governing equations is implemented by the least‐squares method. Equal‐order moving least‐squares approximation is employed with Gauss quadrature in the background cells. The boundary conditions are enforced by the penalty method. The matrix‐free element‐by‐element Jacobi preconditioned conjugate method is applied to solve the discretized linear systems. Cavity flow for steady Navier–Stokes problem and the flow over a square obstacle for time‐dependent Navier–Stokes problem are investigated for the presented least‐squares meshfree method. The effects of inaccurate integration on the accuracy of the solution are investigated. Copyright © 2004 John Wiley & Sons, Ltd.  相似文献   
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