CF4 decomposition over solid ternary mixture NaF-Si-MO（MO=La2O3,CeO2,Pr6O-（11）,Nd2O3,Y2O3）

A solid ternary mixture consisting of NaF,silicon and one metal oxide such as La2O3,CeO2,Pr6O11,Nd2O3,and Y2O3 was prepared and usedas de-fluorinated reagent for CF4 decomposition.The results show that 90% conversion of CF4 can be reached initially over NaF-Si-La2O3,NaF-Si-CeO2,NaF-Si-Nd2O3,and NaF-Si-Y2O3 at 850 C.The fresh and used reagents were characterized using XRD and XPS techniques.It was found that the active components of NaF and metal oxides in NaF-Si-CeO2,NaF-Si-Pr6O11,NaF-Si-Nd2O3,and NaF-Si-Y2O3 weretransformed into inert phases of mixed metal fluorides and silicates,respectively,resulting in an ineffective utilization of these de-fluorinatedreagents,whereas no inert phases from NaF and La2O3 can be observed in the used NaF-Si-La2O3,indicating the NaF-Si-La2O3 reagent couldbe utilized more efficiently than the other reagents in CF4 decomposition.     

Crystal structures of the octahedral rhenium cluster compexes Cs4[Re6S8(OH)6]·6H2O and Cs4[Re6Se8(OH)6]·8H2O

The salts Cs₄[Re₆S₈(OH)₆]·6H₂O (1) and Cs₄[Re₆Se₈(OH)₆]·8H₂O (2) were obtained by the reactions of Re₆S₈Br₂ and Re₆Se₈Br₂ with a CsOH melt with further solution of the products in water and crystallization of 1 and 2 from the aqueous solutions. The structure of the compounds was established by X-ray single crystal diffraction analysis. Compound 1 crystallizes in the orthorhombic space group Pbca with unit cell parameters a = 14.175(2) Å, b = 11.321(2) Å, c = 17.503(2) Å, V = 2808.5(7) ų, Z = 4, d _calc = 5.003 g/cm³; compound 2 crystallizes in the triclinic space group with unit cell parameters a = 9.020(4) Å, b = 9.127(4) Å, c = 10.289(4) Å, α = 79.589(7)°, β = 75.829(7)°, γ = 72.186(7)°, V = 776.8(6) ų, Z = 1, d _calc = 5.402 g/cm³. Original Russian Text Copyright ? 2007 by K. A. Brylev, Yu. V. Mironov, S.-J. Kim, and V. E. Fedorov __________ Translated from Zhurnal Strukturnoi Khimii, Vol. 48, No. 6, pp. 1183–1188, November–December, 2007.     

Synthesis, thermogravimetric analysis, IR spectrum, and the crystal structure of sodium hexatunstomanganate [Na2(H2O)10][Na(H2O)3]2[MnW6O18(OH)6] · 6H2O

The complex [Na₂(H₂O)₁₀][Na(H₂O)₃]₂[MnW₆O₁₈(OH)₆] · 6H₂O was synthesized and studied by mass spectrometry, thermogravimetry, IR spectroscopy, X-ray diffraction. The crystals are monoclinic, space group P2₁/n, a = 11.698(2), b = 11.670(2), c = 14.652(3) ?, β = 102.52(3)°, V = 1952.7(7) ?³, ρ(calcd.)= 3.45 g/cm³, Z = 2.     

SO2, HCl, CO2, HS und S?urechloride

Ohne Zusammenfassung     

Functionalised tetraarylstannanes Sn[C6H4-R]4 (R=-CH(CH2O)2, -CHO, -COOH, -CHN-NH-C6H3-2,4-(NO2)2, -CH2OH, -CO-NH-CH2-COO-CH3, -CH[N(C2H4)2O]2)

Reaction of tin tetrachloride with the appropriate Grignard reagent gave Sn[C₆H₄-CH(OCH₂)₂]₄ (2), which was transformed to Sn[C₆H₄-CHO]₄ (3) and its hydrazido and amino derivatives Sn[C₆H₄-CHN-NH-C₆H₃-2,4-(NO₂)₂]₄ (5) and Sn{C₆H₄-CH[N(C₂H₄)₂O]₂}₄ (8). Oxidation of (3) produced Sn[C₆H₄-COOH]₄ (4) while reduction of (3) gave Sn[C₆H₄-CH₂-OH]₄ (6). From the acid 4, an amino acid Sn[C₆H₄-CO-NH-CH₂-CO-OCH₃]₄ (7) could be obtained by reaction with the methyl ester of glycine. All compounds were isolated in pure form with yields of 40-64% and were characterised by spectroscopic means (heteronuclear NMR) or by X-ray structure determination (3).     

Facile synthesis and X-ray structures of (η-C5Me5)Ti(OAr)3 (OAr = OC6F5, OCH2C6F5, and OCH2C6F2H3)

New half-sandwich titanocene complexes (η⁵-C₅Me₅)Ti(OC₆F₅)₃ (1), (η⁵-C₅Me₅)Ti(OCH₂C₆F₅)₃ (2), and (η⁵-C₅Me₅)Ti(OCH₂C₆F₂H₃)₃ (3) were synthesized via the displacement of methoxide ligands in (η⁵-C₅Me₅)Ti(OMe)₃ by the corresponding aryloxy or benzyloxy ligands. These compounds have been fully characterized by various spectroscopic methods including X-ray crystallography. Compound 1 has a distorted three-legged piano stool structure. However, complexes 2 and 3 have the chariot-like structure, where chariot means a two-wheeled horse-drawn vehicle. The π electron donation of oxygen atom to Ti center in complexes 1-3 is considerable.     

Solvothermal indium fluoride chemistry: Syntheses and crystal structures of K5In3F14, β-(NH4)3InF6 and [NH4]3[C6H21N4]2[In4F21]

The solvothermal syntheses and crystal structures of three indium fluorides are presented. K₅In₃F₁₄ (1) and β-(NH₄)₃InF₆ (2) are variants on known inorganic structure types chiolite and cryolite, respectively, with the latter exhibiting a complex and apparently novel structural distortion. [NH₄]₃[C₆H₂₁N₄]₂[In₄F₂₁] (3) represents a new hybrid composition displaying a unique trimeric metal fluoride building unit.     

Large-bite bisphosphite, 1,3-C6H4{OPOC10H6(μ-S)C10H6O}2: Synthesis, copper(I), and gold(I) complexes

Large-bite bisphosphite ligand 1,3-C₆H₄{OPOC₁₀H₆(μ-S)C₁₀H₆O}₂ (3), is obtained by reacting chlorophosphonite {OC₁₀H₆(μ-S)C₁₀H₆O}PCl (2) with resorcinol in the presence of triethylamine. Treatment of 3 with CuCl in 1:1 molar ratio produces a 1D-coordination polymer [CuCl{(-OC₁₀H₆(μ-S)C₁₀H₆O-)P(-OC₆H₄O-)P(-OC₁₀H₆(μ-S)C₁₀H₆O-)}-κP,κP]_∞ (4) in good yield. Similar reaction of 3 with two equivalents of AuCl(SMe₂) affords a dinuclear complex, [Au₂Cl₂{(-OC₁₀H₆(μ-S)C₁₀H₆O-)P(-OC₆H₄O-)P(-OC₁₀H₆(μ-S)C₁₀H₆O-)}-κP,κP] (5). Single crystal X-ray structures of the ligand 3 and the complexes 4 and 5 are reported. The gold complex 5 shows dimeric structure supported by strong Au···Au aurophilic interactions.     

[{Pt4(en)4(NHCOtBu)4}{Tl(18-crown-6)}2](PF6)6的合成与晶体结构

The compound [{Pt₄(en)₄(NHCO^tBu)₄}{Tl(18-crown-6)}₂](PF₆)₆ has been synthesized by a simple one-pot multicomponent reaction. Its structure was determined by X-ray single crystal diffraction analysis. The cation of the compound consists of one linearly arranged [Pt₄(en)₄(NHCO^tBu)₄]⁴⁺ chain and two [Tl(18-crown-6)]⁺ ions located at the two ends of the platinum chain. The complex crystallizes in a triclinic P1 with a=1.060 5(1), b=1.252 3(1), c=2.015(2) nm, α=107.430(2)°, β=91.032(2)°, γ=101.910(2)°, V=2.489 6(4) nm³, Z=2, R₁=0.074 4, wR₂(I>2σ(I))=0.222 5, S=1.062. CCDC: 294083.     

低温下Na //Cl-,SO42-,NO3-,H2O体系相平衡研究

采用等温溶解平衡法研究了四元体系Na+//Cl-,SO42-,NO-3-H2O在5、0、-5与-15℃下的相平衡关系。结果表明,4个温度下体系无复盐形成,平衡相图的构型基本一致;平衡相图均由3个结晶区(Na2SO4·10H2O、Na Cl和Na NO3)、3条单变量曲线(Na Cl-Na2SO4·10H2O、Na Cl-Na NO3、Na NO3-Na2SO4·10H2O)及1个共饱点(Na Cl-Na NO3-Na2SO4·10H2O)组成;4个温度下的平衡相图相比,随着温度的下降Na2SO4·10H2O结晶区不断扩大,Na Cl和Na NO3结晶区相对缩小;与该体系常温下的平衡相图相比,由于无复盐形成,低温下的相图大为简化。     

Kinetics of the radical reactions in pulse radiolyzed RHF — CO2(SF6)-O2-NO gaseous mixtures; RHF = CH3CH2F, CH3CHF2, CH3CF3, CH2FCF3

The kinetics of the peroxy radicals RHFO₂ reactions with NO has been studied by using pulse radiolysis and UV absorption spectroscopy. The rate constants of interaction of oxygen atoms with NO − k ₂ = 2.2±0.2·10⁻¹² cm³·s⁻¹ and NO₂ − k ₃ = 2.1±0.2·10⁻¹¹ cm³·s⁻¹ were found in agreement with the literature values. The bath gases (SF₆ or CO₂) have got minor effect on the rate constants of RHFO₂+NO→NO₂+prod. reactions; RHFO₂ = CH₃CH₂O₂, CH₃CHFO₂, CH₃CF₂O₂, CF₃CH₂O₂, CF₃CHFO₂. The obtained rate coefficients are in the scope of the literature values, although they are lower than those recommended in NIST database. The reasons are discussed.     

Ln(η6-m-C6H4Me2)(AlCl4)3, (Ln=Pr,Er)的合成及Pr配合物的晶体结构

LnCl₃(Ln=Pr,Er)与AlCl₃在二甲苯中反应，合成了η⁶-(m-Me₂C₆H₄)Ln(AlCl₄)₃这两个新配合物并对其进行了元素分析、红外光谱和质谱的表征。测定了Pr配合物的晶体结构。该配合物具有扭曲的五角双锥几何构型。二甲苯和一个氯原子处于两个顶点，Pr配合物属单斜晶系，空间群P相似文献   

Double complex salts [Pd(NH3)4]3[Rh(NO2)6]2, [Pd(NH3)4]3[Rh(NO2)6]2·H2O as promising precursors to prepare Pd-Rh nanoalloys

Two new double complex salts [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂ (I) and [Pd(NH₃)₄]₃[Rh(NO₂)₆]₂·H₂O (II) are synthesized and characterized. The techniques to produce one-phase residues of the salts are developed. The crystallographic data for I: a = 18.915(2) ?, V = 6767.4 ?³, F-43c space group, Z = 8, d _x = 2.548 g/cm³; II: a = 21.160(6) ?, b = 8.085(7) ?, c = 21.363(4) ?, β = 91.71(4)°, V = 3661.1(6) ?³, P2₁/c space group, d _x = 2.357 g/cm³. Thermal properties of the obtained compounds in the hydrogen and helium atmosphere are studied. It is shown that the final product of their decomposition both in the inert and reducing atmosphere is a powder consisting of bimetallic nanosized particles (nanoalloy) of Pd_0.59Rh_0.41 (Fm-3m space group, a = 3.856(2) ?, crystallite size of 8–11 nm).     

L-丙氨酸在LiNO3, NaNO3, KNO3和NaClO4水溶液中的体积性质

利用Anton Paar DMA 55精密数字密度计测定了L-丙氨酸在LiNO₃, NaNO₃, KNO₃和NaClO₄水溶液中的密度, 计算了L-丙氨酸的表观摩尔体积、极限偏摩尔体积、迁移偏摩尔体积、理论水化数和体积作用系数. 根据静电相互作用和结构水合作用模型讨论了阴离子和阳离子对迁移偏摩尔体积的影响. 结果表明, L-丙氨酸在四种含氧酸盐水溶液中的迁移体积均为正值, 并且随着盐浓度的增大而增大. L-丙氨酸两性离子端基和阴阳离子间的静电作用对迁移体积的贡献是主要的. 静电作用削弱了两性离子带电中心对周围水分子的电致收缩效应, 造成了理论水化数随溶液浓度的增加而减小. L-丙氨酸在NaNO₃, KNO₃和NaClO₄水溶液中迁移体积的不同主要是由于静电作用的不同引起的, 在LiNO₃水溶液中迁移体积的“反常”是由于结构相互作用的影响较大所致.     

New aromatic pentafluoro-λ-sulfanyl (SF5) derivatives, m-SF5(CF2)2C6H4X: (X = N3, Br, OC(O)CHCH2, CHCH2)

Preparation of the following new m-SF₅CF₂CF₂C₆H₄X derivatives has been achieved: X=N₃(2), Br(3), OC(O)CHCH₂(4), CHCH₂(5). The compounds were characterized by their respective IR, NMR, mass spectra (MS) and high resolution mass spectrometry (HRMS). An improved yield of SF₅(CF₂)₂C₆H₅ (1) is also reported along with the synthesis of the polyacrylate (6) and polystyrene (7) from their respective monomers.     

铁氧簇合物[Fe11O6(OH)6(O2CCH3)15](C5H5N)6的结构和磁性质

通过三核铁盐[Fe₃O(O₂CCH₃)₆(H₂O)₃]C1在吡啶溶液中水解聚合得到铁氧簇合物[Fe₁₁O₆(OH)₆(O₂CCH₃)₁₅](C₅H₅N)₆。晶体结构表明11个铁离子(Ⅲ)中6个位于扭曲的三棱柱的顶点上，其余5个分别位于三棱柱的每个面之外。铁离子(Ⅲ)之间以氧桥或者羟基氧桥相连。变温磁化率证实铁离子(Ⅲ)之间是反铁磁耦合的。     

甲基对硫磷-D6的合成

报道了一种合成甲基对硫磷-D₆的新方法。以三氯硫磷、氘代甲醇和对硝基苯酚为起始原料,经三次酯化反应合成了目标产物甲基对硫磷-D₆,总收率47.6%,其结构经¹H NMR、 ¹³C NMR、 ³¹P NMR和HR-MS(ESI)确证。     

N6H6结构和性质的理论研究

采用密度泛函理论的b3lyp方法在6-311＋＋G**基组上对15种分子式为N₆H₆的氮氢化合物进行了理论计算, 并且应用了自然键轨道理论(Nature Bond Orbital, NBO)和分子中的原子理论(Atoms In Molecules, AIM)分析了这些化合物的成键特征和相对稳定性. NBO分析表明N原子孤对电子到相邻的氮氮键的超共轭作用是影响氮氮键长变化的主要因素, AIM计算的氮氮键的键临界点电荷密度与键长呈反比关系. 而且, NBO的立体和超共轭分析表明立体交换排斥能和超共轭作用对这些分子的相对稳定性起了重要作用. G3MP2计算结果表明氮氢化合物的生成热均为正, 并且环状分子的能量和生成热都高于链状分子.     

N6H6结构和性质的理论研究

采用密度泛函理论的b3lyp方法在6-311＋＋G**基组上对15种分子式为N₆H₆的氮氢化合物进行了理论计算, 并且应用了自然键轨道理论(Nature Bond Orbital, NBO)和分子中的原子理论(Atoms In Molecules, AIM)分析了这些化合物的成键特征和相对稳定性. NBO分析表明N原子孤对电子到相邻的氮氮键的超共轭作用是影响氮氮键长变化的主要因素, AIM计算的氮氮键的键临界点电荷密度与键长呈反比关系. 而且, NBO的立体和超共轭分析表明立体交换排斥能和超共轭作用对这些分子的相对稳定性起了重要作用. G3MP2计算结果表明氮氢化合物的生成热均为正, 并且环状分子的能量和生成热都高于链状分子.     

X-ray study of the thermolysis products of (NH4)2[OsCl6]x[PtCl6]1?x

Thermolysis of the complex salts (NH₄)₂[OsCl₆] _x [PtCl₆]_1−x (x = 0.25−0.9) formed nanocrystalline Os _x Pt_1−x phases. Pseudomorphism has been found: the habit of the single crystals of the starting salts is preserved during thermolysis, and the ∼10–20 nm metal particles are agglomerated into octahedral structures sized 5–10 μm.