Ba(OH)2 as catalyst in organic reactions, III. The structure of adsorbed ylids

The nature of adsorbed sulfonium and phosphonate ylids on a new barium hydroxide catalyst (C-200) is analyzed by IR. The catalytic activity of C-200 in solid-liquid phase transfer conditions is explained by these IR studies.

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(C-200) . C-200 - .

     

Ba(OH)2 as catalyst in organic reactions: I. Nature of active sites in the michael addition

In order to determine the nature of active sites that act in the Michael addition of ethyl malonate to chalcone in EtOH, catalyzed by activated barium hydroxide, selective poisoning experiments have been carried out. It has been found that the catalytic activity of the C-200 catalyst is related to the strong basic sites titrated by TBMPHE.

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, - . , C-200 - , TBMPHE.

     

Ba(OH)2 catalyst in organic reactions, XIII. Oxidation of benzyl halides to benzaldehydes

The oxidation of benzyl halides by DMSO in presence of barium hydroxide as catalyst in the heterogeneous phase is described. The reaction is optimized. The influence of halide and benzyl halide ring substituent on the yield is discussed. The mechanism for the heterogeneous process is discussed.

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, . . . .

     

The nature of active sites in Ba(OH)2 catalyst

A general and repetitive method to determine the base strength and number of basic sites of catalysts with low surface area is reported. The nature of the titrating agent is discussed. The nature of the active sites of a Ba(OH)₂ catalyst with low surface area is discussed.

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. . Ba(OH)₂, .

     

Ba(OH)2 as catalyst in organic reactions, part XIV. Michael addition catalyzed by barium complex salts in the homogeneous phase

Michael addition to chalcone is catalyzed by barium complex salts in the homogeneous phase under various conditions. The nature of these intermediates is analyzed. These complex salts are described for the first time. The Michael adduct of malonodinitrile to chalcone is described for the first time.

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, , . . . . .

     

A new Ba(OH)2 catalyst for synthesis of diacetone alcohol

The application of new Ba(OH)₂ catalysts for the preparation of diacetone alcohol is described. No loss of activity is observed when they are stored in a dessiccator over NaOH. The same yield as that described in the literature is obtained, but in a much shorter reaction time (9.5 h against 72–120 h)

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Ba(OH)₂ . NaOH . , , (9,5 72–120 ).

     

Kinetics of self-condensation of acetone over heterogeneous Ba(OH)2 and Sr(OH)2 catalysts

Catalytic performance of Ba(OH)₂ and Sr(OH)₂ in self-condensation of acetone was examined in the temperature range from 273 to 303 K. A kinetic model of second order with respect to acetone was used for interpretation of the results obtained for the diacetone alcohol formation.This revised version was published online in December 2005 with corrections to the Cover Date.     

The reaction of (SO2)2 and (CO2)2 with Ba

The reactions of (CO₂)₂ and (SO₂)₂ with Ba have been investigated using a crossed beam arrangement and the laser-induced fluorescence technique. Internal energy in the BaO product was probed in order to study differences between monomeric and dimeric reactions. The reaction cross section for the dimers of CO₂ was found to be between four and eightfold larger than that of the monomers. This can be explained by the change in the reaction mechanism due to the positive electron affinity of the dimers versus the negative electron affinity of the monomers. The product BaO from the dimeric reactions is much colder rotationally than in the monomeric case. This phenomenon can be explained based on the kinematics.     

La(OH)3和 La2O2CO3纳 米 棒 的 合 成 及 其 催 化 Claisen-Schmidt缩合反应性能简

通过调节溶液的pH值,在水热条件下合成出长径比为2-45的La（OH）₃纳米棒. 对水热合成过程中间体的结构演变分析,发现高碱度有利于小尺寸晶核的形成,La（OH）₃晶体结构的各向异性导致这些晶种沿着C轴方向生长,进而形成纳米棒结构. 将La（OH）₃纳米棒前驱体于773 K焙烧可以得到长径比为2-20的La₂O₂CO₃纳米棒. 随着长径比的增加,La₂O₂CO₃纳米棒暴露的（110）晶面逐渐增加,La³⁺-O^2-碱性位的数目也从0.08增加到0.24 mmol/g. 因此,在Claisen-Schmidt缩合反应中,La₂O₂CO₃纳米棒催化剂上的反应速率随着长径比的增加而逐渐增大.     

Ba(OH)2 as catalyst in organic reactions,IV. Reaction between coumarin and diethyl malonate

The reaction of diethyl malonate and coumarin catalyzed by an activated barium hydroxide catalyst (C-200) in a solid-liquid-system is described. NoMichael addition takes place. An unusual nucleophilic addition-elimination process to the C=O bond of coumarin is observed and the new compound is described the first time. The process is explained by the microcrystalline structure of the solid, the nature of the active sites of the catalyst and the chelating action of coumarin on Ba^II of the lattice.

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Ba(OH)₂ als Katalysator organischer Reaktionen, 4. Mitt.: Die Reaktion zwischen Cumarin und Diethylmalonat

Zusammenfassung Es wird die Reaktion von Diethylmalonat mit Cumarin unter der katalytischen Wirkung von aktiviertem Bariumhydroxid (C-200) in einem Fest-flüssig-System beschrieben. Es ist keineMichael-Addition zu beobachten. Es tritt eine ungewöhnliche Addition-Eliminierung an der C=O-Bindung des Cumarin ein und die dabei entstehende Verbindung wird erstmals beschrieben. Der Prozeß wird auf der Basis der mikrokristallinen Struktur des Festkörpers, der Natur der aktiven Stellen am Katalysator und der chelierenden Wirkung von Cumarin auf die Gitter-Ba^II-Ionen erklärt.

     

Crystal structures of phosphomolybdyl salts: Pb(MoO2)2(PO4)2 and Ba(MoO2)2(PO4)2

Crystal structures of Pb(MoO₂)₂(PO₄)₂ and Ba(MoO₂)₂(PO₄)₂ were determined. Both compounds contain the molybdyl group MoO₂. The monoclinic unit-cell parameters are a = 6.353(7), b = 12.289(4), c = 11.800 Å, β = 92°56(6), and Z = 4 for the lead salt and a = 6.383(8), b = 7.142(7), c = 9.953(8) Å, β = 95°46(8), and Z = 2 for the barium salt. $\text{P2}{}_1\text{c}$ is the common space group. The R values are respectively R = 0.027 and R = 0.031 for 1964 and 1714 independent reflections. The frameworks built up by a three-dimensional network of monophosphate PO₄ and molybdyl MoO₂ groups are similar, characterized mainly by corner-sharing PO₄ and MoO₆ polyhedra. Two oxygen atoms of each MoO₆ group are bonded to the molybdenum atom only as in other molybdyl salts.     

Ba3 (VO4)2-K2 Ba(MoO4)2 and Pb3 (VO4)2-K2 Pb(MoO4)2 systems

Phase equilibria in the Ba₃(VO₄)₂-K₂Ba(MoO₄)₂ and Pb3(VO₄)₂-K₂Pb(MoO₄)₂ systems have been investigated. In the first system, a continuous series of substitutional solid solutions with the palmierite structure is formed, and in the second one, the polymorphic transition in lead orthovanadate at 100°C restricts the extent of the palmierite-type solid solution to 10–100 mol % K₂Pb(MoO₄)₂. Original Russian Text ? V.D. Zhuravlev, Yu.A. Velikodnyi, A.S. Vinogradova-Zhabrova, A.P. Tyutyunnik, V.G. Zubkov, 2008, published in Zhurnal Neorganicheskoi Khimii, 2008, Vol. 53, No. 10, pp. 1746–1748.     

Condensation reaction through base assistance within (Ph2SiO)8[AlO(OH)]4

When the polycyclic alumosiloxane (Ph₂SiO)₈[AlO(OH)]₄, which may be isolated as the diethyl ether adduct (Ph₂SiO)₈[AlO(OH)]₄·4OEt₂, is allowed to react with the double N-methylpiperidine (nmp) adduct of monochloroalane, AlH₂Cl·2nmp (1) (crystal structure analysis), the polycycle (Ph₂SiO)₈[AlO(O)_0.5]₄·2nmp (2) is obtained. Compared to the starting material and apart from the coordinating bases, the compound formally has lost two water molecules. The structure of (Ph₂SiO)₈[AlO(O)_0.5]₄·2nmp (2) can be derived from (Ph₂SiO)₈[AlO(OH)]₄ by substituting the central Al₄(OH)₄ motif through an Al₄O₂ entity which consists of a central Al₂O₂ ring coordinated to two further aluminum atoms through almost trigonal planar oxygen atoms. Using tris(ethylene)diamine (ted) as base and reacting it with (Ph₂SiO)₈[Al(OH)]₄, we have been able to isolate and completely characterize an intermediate on the way to these formally condensed alumosiloxane polycycles like in (Ph₂SiO)₈[AlO(O)_0.5]₄·2nmp (2). It has the composition (Ph₂SiO)₈[AlO(O)_0.25]₄·(OH·ted)₂·(OH₂·ted) (3) and has, compared to the starting material, the same number of hydrogen, oxygen, aluminum and silicon atoms within the inner molecular framework. Nevertheless, its structure is very different: whereas half of the molecule is structurally similar to (Ph₂SiO)₈[AlO(OH)]₄, with OH-groups forming hydrogen bridges to the nitrogen atoms of ted and connecting two aluminum atoms, the other half contains a unique oxygen atom which is in an almost planar trigonal bonding mode to three aluminum atoms. Furthermore, this part of the molecule has an aluminum atom to which a water molecule is coordinated, one of the hydrogen atoms being involved in hydrogen bonding to a further tris(ethylene)diamine (ted). This structure gives some important insights in the possible mechanism of the “condensation reaction” within (Ph₂SiO)₈[AlO(OH)]₄.     

Cluster condensation reactions. The synthesis and crystal and molecular structure of Os6(CO)14(μ2-PPh2)2(μ3-S)3(μ4-S)

Thermal degradation of the cluster compound Os₃(CO)₈(PPh₂H)(μ₃-S)₂ (I) at 125°C leads to decarbonylation and formation of the new ligand bridged hexanuclear cluster Os₆(CO)₁₄(μ-PPh₂)₂(μ₃-S)₃(μ₄-S) (II) in 11% yield. Space Group: P$\text{1}$, No. 2, a 10.427(5), b 13.552(3), c 17.919(3) Å, α 84.87(2), β 75.41(3), γ 78.43(3)°, V 2399(2) ųZ = 2, _?calc 2.82 g cm^?3. The structure was solved by the heavy atom method and refined (3223 reflections) to the final residuals R = 0.042 and R_w = 0.036. The molecule consists of two sulfido bridged open triosmium clusters which are linked by a bridging sulfido ligand and a bridging diphenylphosphino ligand.     

混合纳米氢氧化镍的球镍电极材料的电化学活性研究

采用配位沉淀法制备出了Ni(OH)₂样品，经XRD测试为β-Ni(OH)₂，TEM测试结果表明其为平均粒径50nm左右的不规则的颗粒。将所制备的纳米Ni(OH)₂按8wt%的比例在球镍中混合后制成电极，可使正极的比容量提高11%左右。热分析表明，纳米Ni(OH)₂的电化学活性高于球镍的电化学活性。激光拉曼光谱的测试结果说明了8wt%混合后制成的纳米电极确实有较好的放电容量，同时也证实了用拉曼光谱可以表征电极材料的充放电     

Thermal analysis of β-Co2(OH)3Cl and Zn5(OH)5Cl2 · H2O

Samples of β-Co₂(OH)₃Cl and Zn₅(OH)₈Cl₂ · H₂O have been prepared and their thermal decomposition studied in air and N₂ by DTA and TG up to 1000°C. X-Ray diffraction analysis of the thermal treatment products in air at various temperatures from 100 to 100°C was also carried out. The results obtained made it possible to establish the steps through which the pyrolysis of both compounds proceeds.     

Computational comparison of Rh2(esp)2 and Rh2(O2CH)4 as catalysts in a carbenoid reaction

A computational study of Rh₂(esp)₂-catalysed cyclopropanation of styrene with ethyl bromodiazoacetate is presented. The calculated structures and the energy profile of the reaction show a high level of similarity between Rh₂(esp)₂, a catalyst with sizeable, tethered ligands, and the simplified model catalyst Rh₂(O₂CH)₄.     

Claisen-Schmidt condensation reaction on BaO-ZrO2 mixed oxides

A series of BaO-ZrO₂ mixed oxides has been prepared by the sol-gel method. Crystalline structures were observed by XRD in the mixed oxides. High selectivity to chalcone and benzoic acid as by-products was obtained by performing the acetophenone-benzaldehyde condensation reaction. For both reactions a basic heterogeneous catalytic mechanism was suggested.     

煤中负载氢氧化钙对催化气化和甲烷化反应的影响

以不连沟次烟煤为研究对象,在加压固定床中研究Ca(OH)_2对煤气化及负载Ca(OH)_2煤热解半焦的甲烷化反应活性。结果表明,煤中添加Ca(OH)_2能够明显促进气化反应的进行和甲烷的生成,随着气化温度的升高和负载量的增加,碳转化率增加,但负载量存在饱和点。不同的催化剂负载方式对Ca的分散有一定的影响,进而影响其催化性能。含有Ca的半焦能够明显促进甲烷化的进行,出口气甲烷含量随甲烷化温度和催化剂负载量的升高而增强。采用红外光谱分析揭示了煤负载Ca(OH)_2的离子交换机理和扩散过程,这一过程影响煤气化反应性能。     

球型Ni(OH)2表面包覆Y(OH)3及其高温充放电性能

应用共沉淀的方法在球型Ni(OH)₂的表面包覆了一层Y(OH)₃,并研究了包覆不同含钇量后的球型Ni(OH)₂的高温充放电性能。研究结果表明:包覆Y(OH)₃的球型Ni(OH)₂具有良好的高温充放电性能。其中1C充放电条件下,包覆量为0.3%的Ni(OH)₂较好,0.2C充放电条件下,包覆量为1%的Ni(OH)₂较好。