Solvent-dependent formation of di- and trinuclear rhodiurn and iridium complexes bridged by N,N '-donor ligands

Reactions of Rh and Ir hydrido complexes. [Rh(H)(2)(PPh3)(2)(solv)(EtOH)]ClO4 (solv = Me2CO, 1a; EtOH, 1b) and [Ir(H)(2)(PPh3)(2)(Me2CO)(2)]BF4 (2), with various N,N'-donor bridging ligands, such as pyrazine (pyz), 4,4'-trimethylenedipyridine (tmdp) and di(4-pyridyl) disulfide (dpds), in some solvents were examined, and their reaction products were characterized by X-ray crystal structure analysis. IR, H-1 NMR and UV-vis spectra. Rh hydrido complexes, la or 1b, formed a dinuclear Rh complex, [Rh-2(PPh3)(2) {(eta(6)-C6H5PPh2}(2)] (ClO4)(2).6CH(2)Cl(2) (3.6CH(2)Cl(2)), in dichloromethane with a reductive elimination of hydrogen. The reactions of 1a or 1b with the pyz ligand in dichloromethane and tetrahydrofuran gave triangular Rh-3 complexes, [Rh-3(PPh3)(6)(pyz)(3)](ClO4)(3).CH2Cl2 (5.CH2Cl2) and [Rh-3(PPh3)(6)(pyz)(3)](ClO4)(3).EtOH (5.EtOH), respectively, in contrast to the formation of a dinuclear Rh hydrido complex, [Rh-2(H)(4)(PPh3)(4)(Me2CO)(2)(pyz)](ClO4)(2).EtOH A-EtOH). in acetone. The reactions of la or 1b with the tmdp ligand in dichloromethane and 3-methyl-2-butanone also afforded dinuclear Rh complexes, [Rh-2(PPh3)(4)(tmdp)(2)](ClO4)(2) (6) and [Rh-2(PPh3)(4)(tmdp)(2)](ClO4)(2).4MeCOCHMe(2) (6.4MeCOCHMe(2)), respectively. On the other hand, Ir hydrido complex 2 reacted with pyz and dpds ligands in dichloromethane to afford dinuclear Ir complexes, [Ir-2(H)(4)(PPh3)(4)(Me2CO)(2)(pyz)]- (BF4)(2).3CH(2)Cl(2) (7.3CH(2)Cl(2)) and [Ir-2(H)(4)(PPh3)(4)(dpds)(2)](BF4)(2).3CH(2)Cl(2).H2O (8.3CH(2)Cl(2).H2O), respectively, without any reductive elimination of hydrogen. Based on structural studies in solution and in the solid state. it was demonstrated that various Rh and Ir complexes were selectively produced depending on the choice of solvents and N,N'-donor bridging ligands.

Reaction of halfsandwich iridium polychalcogenide complexes with dimethyl acetylenedicarboxylate. Molecular structure of Cp*Ir[S2C2(COOMe)(2)]

The pentamethylcyclopentadienyl iridium complexes Cp*Ir(PMe3)(E-n) (E = S, n = 4, 5 or 6; E = Se, n = 2 or 4 E = Te, n = 2) react with dimethyl acetylenedicarboxylate to give Cp*Ir(PMe3)[E2C2(COOMe)(2)] compounds which tend to lose the trimethylphosphine ligand; the molecular structure of the dithiolene derivative, Cp*Ir[S2C2(COOMe)(2)], has been determined.

The use of half-sandwich iridium dithiolate and diselenolate complexes, Cp*Ir(L)(ER)(2) (L = CO, PMe3, PPh3; ER = SPh, SePh, SeMe), for the synthesis of heterodimetallic compounds. The molecular structure of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)]

Carbonyl-iridium half-sandwich compounds, Cp*Ir(CO)(EPh)(2) (E = S, Se), were prepared by the photo-induced reaction of Cp*Ir(CO)(2) with the diphenyl dichalcogenides, E2Ph2, and used as neutral chelating ligands in carbonylmetal complexes such as Cp*Ir(CO)(mu-EPh)(2)[Cr(CO)(4)], Cp*Ir(CO)(mu-EPh)(2)[Mo(CO)(4)] and Cp*Ir(CO)(mu-EPh)(2)[Fe(CO)(3)], respectively. A trimethylphosphane - iridium analogue, Cp*Ir(PMe3)(mu-SeMe)(2)[Cr(CO)(4)], was also obtained. The new heterodimetallic complexes were characterized by IR and NMR spectroscopy, and the molecular geometry of Cp*Ir(CO)(mu-SePh)(2)[Mo(CO)(4)] has been determined by a single crystal X-ray structure analysis. According to the long Ir...Mo distance (395.3(1) Angstrom), direct metal-metal interactions appear to be absent. (C) 1998 Elsevier Science S.A. All rights reserved.

Microcalorimetric studies of the iridium catalyst for hydrazine decomposition reaction

Microcalorimetric studies of H-2, NH3 and O-2 adsorption, as well as the NH3 decomposition activities evaluation were used to characterize the iridium catalysts for hydrazine decomposition with different supports (Al2O3, SiO,) and iridium contents (1.8, 10.8 and 22.1%). The higher H-2 chemisorption amounts on Ir/Al2O3 catalysts than those on the corresponding Ir/SiO2 counterparts revealed that the strong interaction of iridium and Al2O3 led to higher dispersion of iridium on Ir/Al2O3 catalysts than on Ir/SiO2 catalysts. The larger increase in strong H-2 adsorption sites on highly loaded Ir/Al2O3 than the corresponding Ir/SiO2 ones could be attributed to the interaction not only between iridium atoms but also between iridium and Al2O3. The microcalorimetric results for NH3 adsorption showed that no apparent chemisorption of NH3 existed on Ir/SiO2 catalysts while NH3 chemisorption amounts increased on Ir/Al2O3 catalysts with iridium loadings, which arose from the interaction of the catalysts support of Al2O3 With chloride anion. Both highly dispersed iridium active sites and chloride anion on Ir/Al2O3 catalysts could be beneficial to the intermediate NH3 decomposition in N2H4 decomposition. The similar O-2 plots of differential heat versus normalized coverage on Ir/Al2O3 and Ir/SiO2 catalysts could not be due to the metal-support interaction, but to the formation of strong Ir-O bond. (C) 2005 Elsevier B.V. All rights reserved.

大庆RP-3航空煤油热物性分析

针对广泛应用于超燃冲压发动机的吸热碳氢燃料,简要介绍了用于模拟燃料热物理特性的替代燃料方法和广义对应状态法则.以大庆RP-3航空煤油为例,选择了一个由49%（摩尔比）正十烷,44%1,3,5-三甲基环己烷以及7%正丙基苯组成的替代煤油用来模拟RP-3航空煤油进行热物理特性研究,并采用广义对应状态法则对替代煤油热力学和输运特性进行了数值研究.在此基础上,提出了预测超临界态流体通过音速喷管流量的新方法并得到了实验验证.

受限射流的数值模拟

对柱形燃烧室内的轴对称等温射流流场进行了数值模拟。回流是这类流场的普遍特征。它对于燃烧室火焰的稳定起着重要作用。本文研究了影响回流特征的多种因素。以压力-速度为主要变量,采用K-ε二方程湍流模型进行计算。计算方法的特征之一是膨胀流动的阶梯形边界表示法。结果包括回流区特征及预示的平均流线分布图。计算结果与实验资料相当吻合。这说明了此方法可用于燃烧室性能的分析。

蜂蜡球锥的驻点烧蚀研究

<正> 1.引言 飞行器再入大气层时受热情况严重,表面要发生严重的烧蚀,外形要发生显著的变化,驻点的烧蚀更为严重。这一烧蚀过程能否由蜂蜡这种低温液态层材料在高超音速风洞中再现,能否通过对蜂蜡球锥的驻点烧蚀研究为液态层材料的烧蚀图象形成机理和发展规律提供依据,为两相流问题的理论研究提供实验资料,这便是我们进行蜂蜡球锥驻点烧蚀研究的目的。

带边缘缺口碳纤维增强环氧复合材料静态与疲劳破坏特性

本文对碳纤维增强环氧复合材料0°和±45°铺层无缺口和带直边缺口层板,进行了静态拉伸和拉-拉疲劳破坏试验研究,比较和分析了不同铺层材料和有无缺口试件在静态和疲劳的特性以及损伤破坏型式。采用多种方法(声发射装置、两种位移传感器、电影摄影机、光学显微镜和扫描电镜等),检测层板的损伤。结果表明:带有垂直于载荷方向直边缺口的该类铺层碳/环氧层板受静态或疲劳拉伸时,裂缝不是沿缺口长度方向扩展,而是沿界面(纤维方向)扩展;缺口的存在基本上不影响其余无缺口部分的应力。并讨论了它的损伤破坏机理。

薄层放电的磁流体力学旋转流动分析

<正> 磁流体力学旋转流问题中一般假设流体输运系数为常数。用磁流体力学方法处理电弧放电问题时,经常假设弧柱內外的输运系数分别为两个不同的常数,并取弧柱外介质的电导率为零。在气态裂变反应堆、核火箭及重元素的同位素分离器中,广泛采用交叉电磁场的方法产生等离子体的高速旋转流动。文献[8,9]研究了薄层放电的电磁驱动装置,用多对极实验得到一定的分离效果。可以认为,这类薄层放电的电流集中在

关于动脉血流线性理论的基础

用量纲分析方法分析了动脉脉冲血流线性理论的基础.结论是:1.目前流行的线化条件不适于动脉血流.正确的线化条件应为,或.据此,线性理论适于中等动脉;对主动脉,用以分析压力一流量关系及脉冲波传播特性尚可,不能用来求速度分布.这和实验研究的结论吻合.2.与流动迁移惯性力相比,压力径向梯度的作用是次要的.故在线化条件下考虑径向压力梯度的影响是不必要的.最后用Lou的有限幅度位移模型和最简流动方程给出了解,所得波速公式和计及时一样。

Magnetostatic configuration of a confined magnetic-flux tube

In this paper an isolated magnetic flux tube confined in stratified atmosphere is studied for slender and axisymmetric model. The functions of the pressure, density, and temperature are expanded as a Taylor series of magnetic surface function psi. Several models of an isolated magnetic flux tube confined in a stratified atmosphere are constructed, and the external pressure of the stratified atmosphere decreases reasonably with increasing height. The distribution of thermal dynamic quantities and the magnetic pressure in the flux tube are also obtained.

Non-axisymmetric magnetostatic equilibrium with strong twisted component of magnetic field

The perturbation theory is applied further to the discussion of the equilibrium properties of a sunspot-like magnetic field with a strong twisted component. The basic state reduces to the usual one discussed extensively for the axisymmetric magnetostatic equilibrium with twisted component of magnetic field, and the perturbed state is described by two coupled equations. As the magnetic force-line is twisted, there is a magnetic tension in the azimuthal direction. In this case, the perturbed total pressure is no longer independent of the azimuthal variable θ, and the magnetic field in the dark penumbal fibril may be either stronger or weaker relatively.

饱和水泥试样被爆炸激波损伤破碎的尺度研究

利用水中爆炸冲击波使水泥试样损伤破坏,模拟爆炸采油时激波使岩石损伤开裂的现象.实验获得了适合本实验条件的激波峰压衰减规律p_m≈8.2(~3√W/R~(1.46)),得知压碎区尺度为集中装药特征尺度的2～5倍、拉伸损伤区尺度为集中装药特征尺度的20～30倍,激波使水泥试样破碎、拉裂的能量占总能量的2%～7%.

激光熔覆MoSi_2涂层的研究

本文用高能激光束熔覆MoSi_2粉末在45钢基体上制备了耐高温结构用涂层，用XRD、SEM、EDAX和显微硬度仪分别对熔覆层的组织结构和硬度进行了研究。试验结果表明，由于基体的稀释作用，涂层的相组成为FeMoSi、Fe_2Si和少量的Mo_5Si_3。涂层组织呈现典型的细小枝晶组织特征，枝晶为FeMoSi领先相，枝晶间为FeMoSi和Fe_2Si两相共晶，组织中无孔隙和裂纹等缺陷存在。Mo，Si，Fe线扫描成分布在涂层-基体界面处均缓慢过渡，基体与涂层发生互扩散，为冶金结合。涂层硬度可达HV_(0.5)845，基体硬度为180，涂层硬度比基体提高3.7倍。