Chemoselective reduction of azides catalyzed by molybdenum xanthate by using phenylsilane as the hydride source

A chemoselective, neutral, and efficient strategy for the reduction of azides to corresponding amines catalyzed by dioxobis(N,N,-diethyldithiocarbamato) molybdenum complex (1, MoO2[S2CNEt2](2)) in the presence of phenylsilane is discovered. This chemoselective reduction strategy tolerates a variety of reducible functional groups.

Thermodynamic Properties and Phase Diagram for the System MoO2–TiO2

The activity of molybdenum dioxide (MoO2) in the MoO2–TiO2 solid solutions was measured at 1600 K using a solid-state cell incorporating yttria-doped thoria as the electrolyte. For two compositions, the emf was also measured as a function of temperature. The cell was designed such that the emf is directly related to the activity of MoO2 in the solid solution. The results show monotonic variation of activity with composition, suggesting a complete range of solid solutions between the end members and the occurrence of MoO2 with a tetragonal structure at 1600 K. A large positive deviation from Raoult's law was found. Excess Gibbs energy of mixing is an asymmetric function of composition and can be represented by the subregular solution model of Hardy as follows.The temperature dependence of the emf for two compositions is reasonably consistent with ideal entropy of mixing. A miscibility gap is indicated at a lower temperature with the critical point characterized by Tc (K)=1560 and . Recent studies indicate that MoO2 undergoes a transition from a monoclinic to tetragonal structure at 1533 K with a transition entropy of 9.91 J·(mol·K)−1. The solid solubility of TiO2 with rutile structure in MoO2 with a monoclinic structure is negligible. These features give rise to a eutectoid reaction at 1412 K. The topology of the computed phase diagram differs significantly from that suggested by Pejryd.

Synthesis of metal oxide nanorods using carbon nanotubes as templates

Nanorods of several oxides, with diameters in the range of 10-200 nm and lengths upto a few microns, have been prepared by templating against carbon nanotubes. The oxides include V2O5, WO3, MoO3 and Sb2O5 as well as metallic MoO2, RuO2 and IrO2. The nanorods tend to be single-crystalline structures. Nanotube structures have also been obtained in MoO3 and RuO2.

Microwave-assisted selective deoxygenation of layer- and chain-containing oxides

Very rapid (within 5 min), selective, single-step deoxygenation of layer- and chain-containing oxides, MoO3, CrO3, V2O5, alpha-VOPO4 . 2H(2)O and Ag6Mo10O33 has been accomplished using graphitic carbon in a microwave-assisted reaction. The products were found to be MoO2, Cr2O3, VO2, VPO4 and a mixture of (Ag + MoO2), respectively. Products were characterised by X-ray diffraction (XRD), differential scanning calorimetry (DSC), IR and electron paramagnetic resonance (EPR) spectroscopies. Although conventional methods of preparing these materials are tedious, the present method is simple, fast and yields very homogeneous products of good crystallinity. Our results reveal that while layer- and chain-containing oxides undergo rapid microwave-assisted carbothermal reduction, the non-layered materials do not. The high structural selectivity of these reactions is suggestive of the topochemical nature of the fast reduction process.

Synthesis of layered MoOPO4 center dot 2H(2)O and investigation of its intercalation chemistry

We describe in this paper the synthesis and characterization of a new layered phosphate, MoOPO4 . 2H(2)O (I), and its intercalation chemistry. The phosphate I, crystallizing in a tetragonal structure (a = 6.375(7), c = 7.80(1) Angstrom, and Z = 2) similar to that of VOPO4 . 2H(2)O, has been synthesized by the reduction of MoO2(HPO4). H2O (II) using ethylene glycol in an CH3CN medium at similar to 60 degrees C. Interestingly, I could be readily oxidized back to II using Br-2 in CH3CN at room temperature. Considering the close structural relationship existing between I and II, it is likely that the reduction and oxidation of the phosphates proceed by a topotactic mechanism. I is a novel layered host intercalating a variety of organic bases such as n-alkylamines, pyridine, and aniline, mainly through an acid-base interaction. Unlike VOPO4 . 2H(2)O, I does not exhibit reductive intercalation reactivity.

Reaction of La2CuO4 with binary metal oxides in the solid state: Metathesis, addition, and redox metathesis pathways

Investigation of the reaction of La2CuO4 with several binary metal oxides in the solid state at elevated temperatures has revealed three different reaction pathways. Reaction of La2CuO4 with strongly acidic oxides such as Re2O7, MoO3, and V2O5 follows a metathesis route, yielding a mixture of products: La3ReO8/La2MoO6/LaVO4 and CuO. Oxides such as TiO2, MnO2, and RuO2 which are not so acidic yield addition products: La2CuMO6 (M = Ti, Mn, Ru). SnO2 is a special case which appears to follow a metathesis route, giving La2Sn2O7 pyrochlore and CuO, which on prolonged reaction transform to the layered perovskite La2CuSnO6. The reaction of La2CuO4 with lower valence oxides VO2 and MoO2, on the other hand, follows a novel redox metathesis route, yielding a mixture of LaVO4/LaCuO2 and La2MoO6/Cu, respectively. This result indicates that it is the redox reactivity involving V-IV + Cu-II --> V-V + Cu-I and Mo-IV + Cu-II --> Mo-VI + Cu-0, and not the acidity of the binary oxide, that controls the nature of the products formed in these cases. The general significance of these results toward the synthesis of complex metal oxides containing several metal atoms is discussed.

Solubility and activity of oxygen in liquid nickel in equilibrium with -Al2O3 and NiO.(1+x)Al2O3

The limiting solubility of oxygen in liquid nickel in equilibrium withα-alumina and nickel aluminate has been measured by inert gas fusion analysis of suction samples in the temperature range 1730 to 1975 K. The corresponding oxygen potential has been monitored by a solid electrolyte cell consisting of calcia stabilized zirconia as the electrolyte and Mo + MoO2 as the reference electrode. The results can be summarized by the following equations: log(at. pct O) = \frac - 10,005T + 4.944 ( ±0.015)log(atpctO)=T−10005+4944(0015) % MathType!MTEF!2!1!+-% feaafiart1ev1aaatCvAUfeBSjuyZL2yd9gzLbvyNv2CaerbuLwBLn DmO2 /4.606RT = log P O2 1/2 = \frac - 13,550T + 4.411 ( ±0.009)O24606RT=logPO212=T−13550+4411(0009) From simultaneous measurements of the potential and concentration of oxygen in melts, not in thermodynamic equilibrium with alumina and aluminate phases, information on the composition dependence of the activity coefficient and the standard free energy of solution of oxygen is obtained. For the reaction, $\frac{1}{2} O_2 \to \underset{\raise0.3em\hbox{$Missing close brace ΔG o = -72,930 - 7.11T (±840) J gr.at.–1 = + 0.216 at. pct OlogfO=T−500+0216atpctO where the standard state for dissolved oxygen is that which makes the value of activity equal to the concentration (in at. pct) in the limit as concentration approaches zero. The oxygen solubility in liquid nickel in equilibrium with solid NiO, evaluated from thermodynamic data, is compared with information reported in the literature. Implications of the results to the deoxidation equilibria of aluminum in nickel are discussed.

Mixed-ligand aroylhydrazone complexes of molybdenum: Synthesis, structure and biological activity

The reaction of the benzoylhydrazone of 2-hydroxybenzaldehyde (H2L) with MoO2(acac)(2)] proceeds smoothly in refluxing ethanol to afford an orange complex MoO2L(C2H5OH)] (1). The substrate binding capacity of 1 has been demonstrated by the formation and isolation of two mononuclear MoO2L(Q)] {where Q = imidazole (2a) and 1-methylimidazole (2b)} and one dinuclear (MoO2L)(2)(Q)] {Q = 4,4'-bipyridine (3)} mixed-ligand oxomolybdenum complex. All the complexes have been characterized by elemental analysis, magnetic and spectroscopic (IR, UV-Vis and NMR) measurements. The molecular structures of all the oxomolybdenum(VI) complexes (1, 2a, 2b and 3) have been determined by X-ray crystallography. In each complex, the dianionic planar ligand is coordinated to the metal centre via one enolate oxygen, one phenolate oxygen and an azomethine nitrogen atom. The complexes have been screened for their antibacterial activity against Escherichia coli, Bacillus and Pseudomonas aeruginosa. The minimum inhibitory concentration of these complexes and their antibacterial activity indicates that compounds 2a and 2b are potential lead molecules for drug designing. (C) 2012 Elsevier Ltd. All rights reserved.

Synthesis, structural studies and catalytic activity of dioxidomolybdenum(VI) complexes with aroylhydrazones of naphthol-derivative

Reaction of the salicylhydrazone of 2-hydroxy-1-naphthaldehyde (H2L1), anthranylhydrazone of 2hydroxy-l-naphthaldehyde (H2L2), benzoylhydrazone of 2-hydroxy-1-acetonaphthone (H2L3) and anthranylhydrazone of 2-hydroxy-1-acetonaphthone (H2L4; general abbreviation H2L) with MoO2(acac)21 afforded a series of 5- and 6- coordinate Mo(VI) complexes of the type MoO2L1-2(ROH)] where R = C2H5 (1) and CH3 (2)], and MoO2L3-4] (3 and 4). The substrate binding capacity of 1 has been demonstrated by the formation of one mononuclear mixed-ligand dioxidomolybdenum complex MoO2L1(Q)] (where Q= gamma-picoline (la)). Molecular structure of all the complexes (I, la, 2,3 and 4) is determined by X-ray crystallography, demonstrating the dibasic tridentate behavior of ligands. All the complexes show two irreversible reductive responses within the potential window -0.73 to -1.08 V, due to Movl/Mov and Mov/Mow processes. Catalytic potential of these complexes was tested for the oxidation of benzoin using 30% aqueous H2O2 as an oxidant in methanol. At least four reaction products, benzoic acid, benzaldehydedimethylacetal, methyl benzoate and benzil were obtained with the 95-99% conversion under optimized reaction conditions. Oxidative bromination of salicylaldehyde, a functional mimic of haloperoxidases, in aqueous 1-1202/KEr in the presence of HC1O4 at room temperature has also been carried out successfully. (C) 2013 Elsevier Ltd. All rights reserved.

高温高压和不同氧逸度条件下斜方辉石电导率的实验研究

在1．0～4．0GPa和1073～1423K及不同的氧分压条件下，借助YJ-3000t紧装式六面顶高压设备和Sarltron-1260阻抗／增益-相位分析仪，就位测定了斜方辉石的电导率。氧逸度控制由Ni＋NiO、Fe＋Fe3O4、Fe＋FeO和Mo＋MoO2四种固态氧缓冲剂完成的。实验结果表明：①在所选择的频率范围内（10^-1～10^6Hz），复阻抗对频率有很强的依赖性;②随着温度（T）升高，电导率（σ）增大，logσ与1／T之间符合Arrenhius关系.

高温高压和不同氧逸度控制下单晶橄榄石电导率的实验研究

在1．0—4．0GPa，1123—1473K和控制氧逸度（Ni＋NiO，Fe＋Fe3O4，Fe＋FeO和Mo＋MoO2等4种氧缓冲剂）的条件下，借助YJ-3000t紧装式六面顶高温高压设备和Sarhron-1260阻抗／增益-相位分析仪，就位测定了橄榄石的电导率．实验结果表明：（1）在测定的频率范围（10^3-10^6Hz），样品的电导率对频率具有很强的依赖性；（2）随着温度（T）升高，电导率（σ）增大，lgσ与1／T之间符合Arrhenius关系；（3）在Fe＋Fe3O4氧缓冲条件下，随着压力升高，电导率降低，而活化焓和指前因子增大，并给出样品的活化能和活化体积分别为（1．25±0．08）eV和（0．105±0．025）cm^3·mol；（4）在给定的压力和温度下，随着氧逸度增加，电导率增大，活化焓降低；（5）小极化子导电机制可为橄榄石在高温高压下的导电行为提供合理的解释.

高温高压和不同氧逸度下上地幔矿物岩石电导率的实验研究

借助于YJ-3000t六面顶高压设备和Solartron-1260阻抗/增益相位分析仪，在1.0~4.0 GPa和1073~1473 K及NNO (Ni+NiO)、IM (Fe+Fe3O4)、IW (Fe+FeO) 和MMO (Mo+MoO2) 4种固态氧缓冲剂控制氧分压条件下就位测量了单晶辉石、辉石岩、单晶橄榄石和二辉橄榄岩的电导率。取得如下结果： 1、在实验选择的频率范围10-1~107 Hz，无论从阻抗谱的Nyquist图还是Bode图均可以看出，电导率对频率具有很强的依赖性； 2、随着温度升高，电导率增大，Lg σ与1/T之间符合Arrhenius线性关系式； 3、在 IM和NNO固态氧缓冲约束条件下，随着压力升高，电导率降低，获得了一系列表征样品体系载流子特征的指前因子、活化能、活化焓和活化体积等Arrhenius参数； 4、在给定压力和不同氧缓冲剂控制下，按照NNO、IM、IW和MMO氧逸度降低的顺序，电导率减小； 5、在2.0 GPa和NNO控制下，按照 (001)、(100)、(010) 的顺序，透辉石的电导率和指前因子减小，活化焓增大，电学性质在不同晶面方向上存在各向异性； 6、样品中的小极化子导电机制可为电导率、指前因子、活化焓和活化体积等随温度、压力及氧逸度的变化规律提供合理解释。

控制热力学条件下的矿物、岩石电学性质研究

电导率是重要的地球物理参数。模拟地球内部条件下的矿物、岩石电导率测量是了解地球内部物质组成及物理化学性质的有效手段，同时，还可以为野外大地电磁测量结果的解释提供依据。在YJ-紧装式六面顶压机上，对原有的矿物、岩石电性测量系统进行了进一步的改进；建立了一套以Solartron 1260阻抗／增益一相位分析仪为测试仪器，使用Mo电极和Mo盾来控制样品氧逸度的测量系统，该系统的氧逸度环境为Mo-MoO2，接近Iw缓冲对。石英（人造水晶）、橄榄石、纯橄榄岩、辉石岩、二辉橄榄岩、巨晶辉石的电导率测量是在新的测量系统下获得的，而辉长岩的电导率测量是基于LCR仪为测量仪器的测试系统下获得的。在压力为1-3GPa、温度为675K-160OK、频率为106-0.1Hz、氧逸度为Mo-MoO2的条件下，对不同方向石英（人造水晶）的电学性质进行了研究。复阻抗平面上出现了反映样品本身性质的阻抗弧和反映样品与电极之间扩散的直线。石英的电导率随温度增加而增加，随压力的变化比较微弱。石英的导电机制主要为离子导电，载流子可能为碱金属离子和氢离子，这些碱金属离子和氢离子主要在平行于光轴的通道中运动。在相同的温度和压力条件下，a石英的电导率和c轴的夹角有关，石英的电导率随着夹角的增大而减小，表现出了强烈的各向异性。对“各个方向石英在发生了相变前后的电导率进行了研究，发现Q石英转变为p石英后，电导率并没有突变，仍然随着温度的增加而增加。在压力为1-2GP。、温度为563-1173K、频率为12-105Hz的条件下研究了辉长岩的阻抗。结果发现辉长岩复阻抗的实部随频率的增加而减小，而虚部随频率增加先增大后减小；相角随频率增加而减小。在复阻抗平面上出现了反映颗粒内部的阻抗弧，该阻抗弧出现在高频段。实验室获得辉长岩在地壳的压力和温度（1.0GP。和893K）条件下的电导率值为1.77×-4S／m，而高导层的电导率值为0-01-0-15S／m，二者相差了2-3个数量级，推断辉长岩不能在下地壳形成高导层。在压力为3.0GPa、温度为1299-1600K、频率为106-0.1Hz、氧逸度为Mo-MoO2条件下，对不同颗粒粒度的橄榄石电导率进行了测量。在复阻抗平面上均出现了反映颗粒内部电响应的阻抗弧，这些阻抗弧随着温度的增加而减小。而反映颗粒边界导电机制的阻抗弧并不明显，两种阻抗弧出现在不同的频率范围内，反映颗粒内部导电机制的阻抗弧出现在频率较高的范围内，而反映颗粒边界导电机制的阻抗弧出现在频率相对低的范围内。不同粒度橄榄石在3.0GPa条件下的电导率随着温度的增加而增加，它们的激化烩介于1.03-2.11ev之间。在压力为1-3GPa、温度为1282-1544K、频率为0.1-106Hz、氧逸度为MO-MoO2的条件下，对纯橄榄岩的电导率进行了测量。在复阻抗平面上出现了反映颗粒内部电响应和颗粒边界电响应的阻抗弧。反映颗粒内部导电的阻抗弧出现在较高的频率段，随着温度的增加，这些阻抗弧逐渐收缩。颗粒边界的阻抗弧出现在相对低的频率段。纯橄榄岩的电导率随着温度增加而增加，随压力变化比较微弱。对颗粒边界的电导率研究表明，颗粒边界的电导率高于颗粒内部的电导率，总电导率则小于颗粒内部和颗粒边界的电导率，颗粒边界并没有增强总电导率。纯橄榄岩的激化能为1，62eV，而激化体积为0.67cm3／mol，指前因子为5125加。利用实验所获得的拟合参数，建立了地球内部200-40Okm处的电导率模型，并同地球物理模型进行了对比，在温度和氧逸度的合理波动范围内，实验室电导率模型和地球物理模型吻合的很好。在压力为1-2GPa、温度为1228-1584K、频率为0.1-106Hz、氧逸度为MO-MoO2条件下，测量了天然和热压辉石岩、热压巨晶辉石、二辉橄榄岩的电导率。结果发现，在复阻抗平面上出现了反映颗粒内部电响应和颗粒边界电响应的阻抗弧，反映颗粒内部导电的阻抗弧出现在较高的频率段，随着温度的增加，这些阻抗弧逐渐收缩。颗粒边界的阻抗弧出现在相对低的频率段。辉石岩、二辉橄榄岩、巨晶辉石电导率随着温度增加而增加，随压力变化比较微弱。天然辉石岩和热压辉石岩颗粒边界的电导率高于它们各自颗粒内部的电导率，而总电导率则小于颗粒内部和颗粒边界的电导率，颗粒边界并没有增强总电导率。辉石岩一二辉橄榄岩一纯橄榄岩的电导率依次减小，这可能是与它们的铁含量有关。天然辉石岩的电导率与热压辉石岩的电导率的差异可能与样品中的水（氢）含量的不同有关。