Surface electron donor properties of Dy2O3, Y2O3 and their mixed oxides with alumina catalyst

The limit of electron transfer in electron affinity from the oxide surface to the electron acceptor (EA) are reported from the adsorption of EA on Dy₂O₃, mixed oxides of Dy₂O₃ with alumina and mixed oxides of Y₂O₃ with -alumina. The extent of electron transfer is understood from magnetic measurements.     

The harmonic force fields of BF3, SnCl4 SbBr3 obtained by the joint use of electron diffraction and vibrational spectroscopy data

The recently developed technique of joint analysis using electron diffraction and vibrational spectroscopy data for determining molecular force fields is demonstrated for the sample molecules BF₃ and SnCl₄. The technique is based on harmonic force constants being the common parameters in the interpretational methods of both components. The general harmonic force field of SbBr₃ is refined in this way using electron diffraction and recently available gas-phase spectroscopic frequencies of vibration.     

The reaction of boron trihalides with CF3Sn(CH3)3 in the presence of trimethylamine

The reaction of CF₃Sn(CH₃)₃ with BCl₃ and BBr₃ in the presence of trimethylamine has been investigated. The volatile adducts CF₂XBF₂·N(CH₃)₃ (X = F, Cl and Br) have been isolated from the complex reaction mixture while the anions BF^?₄, CF₂XBF^?₃, CF₃BF₂CF₂X^? and (CF₂X)₂BF^?₂ have been identified in the residue. [(CH₃)₃NH][CF₂ClBF₃] has been isolated. The formation of the CF₂XB derivatives is likely to occur via CF₂ insertion, which is promoted by the presence of N(CH₃)₃. NMR, IR, Raman and mass spectra of the novel fluoromethyl borane derivatives are reported.     

聚甲基丙烯酸甲酯包覆(CH3NH3) PbBr3纳米晶静电纺丝膜的制备及对氨气的荧光传感

采用原位合成法制备了聚甲基丙烯酸甲酯包覆MAPbBr₃纳米晶（MAPbBr₃@PMMA,MA=甲铵离子）静电纺丝膜。当氨气（NH₃）通入MAPbBr₃@PMMA纤维膜时与MAPbBr₃中的MA发生取代,能显著降低MAPbBr₃@PMMA纤维的荧光强度,以此构建了基于MAPbBr₃@PMMA纤维荧光猝灭的NH₃传感器。通过扫描电镜、透射电镜、粉末X射线衍射和红外对静电纺丝膜的形貌和结构进行表征,通过紫外可见光谱、荧光光谱对其光学特性进行表征。结果表明,传感器的荧光强度与NH₃浓度在8~90 mg·L^-1之间呈现出良好的线性关系（r=0.995 9）,NH₃的检出限低（3 mg·L^-1）,且具有良好的重现性和选择性。在实际样品气体的测定中,加标回收率为92.2%~102.1%,相对标准偏差（RSD）为1.8%~3.2%。     

聚甲基丙烯酸甲酯包覆(CH3NH3)PbBr3纳米晶静电纺丝膜的制备及对氨气的荧光传感

采用原位合成法制备了聚甲基丙烯酸甲酯包覆MAPbBr₃纳米晶(MAPbBr₃@PMMA,MA=甲铵离子)静电纺丝膜。当氨气(NH₃)通入MAPbBr₃@PMMA纤维膜时与MAPbBr₃中的MA发生取代,能显著降低MAPbBr₃@PMMA纤维的荧光强度,以此构建了基于MAPbBr₃@PMMA纤维荧光猝灭的NH₃传感器。通过扫描电镜、透射电镜、粉末X射线衍射和红外对静电纺丝膜的形貌和结构进行表征,通过紫外可见光谱、荧光光谱对其光学特性进行表征。结果表明,传感器的荧光强度与NH₃浓度在8~90 mg·L^-1之间呈现出良好的线性关系(r=0.995 9),NH₃的检出限低(3 mg·L^-1),且具有良好的重现性和选择性。在实际样品气体的测定中,加标回收率为92.2%~102.1%,相对标准偏差(RSD)为1.8%~3.2%。     

Ethylene/1-hexene copolymerization with TiCl4/MgCl2/AlCl3 catalyst in the presence of hydrogen

A TiCl₄/AlCl₃/MgCl₂ (Cat-B) catalyst containing 5.2 wt.% Al was prepared by the reaction of TiCl₄ with ethanol adduct of AlCl₃/MgCl₂ mixture. A TiCl₄/MgCl₂ catalyst (Cat-A) without doped AlCl₃ was also prepared by the same method. Ethylene-1-hexene copolymerization catalyzed by Cat-B in the presence of hydrogen showed slightly higher efficiency and higher 1-hexene incorporation than Cat-A. Comonomer incorporation was markedly increased when the cocatalyst AlEt₃ was replaced by Al(i-Bu)₃. Adding Ph₂Si(OMe)₂ as external donor in the catalyst system caused decrease in polymerization activity and 1-hexene incorporation. Each copolymer sample was fractionated into three fractions: n-heptane insoluble fraction (fraction A), n-heptane soluble and n-hexane insoluble fraction (fraction B) and n-hexane soluble fraction (fraction C). In most cases the amount of intermediate fraction (fraction B) was smaller than the other fractions and did not increase as the total 1-hexene content increase, indicating the presence of two classes of copolymer fractions with greatly different comonomer content and clear bimodality of the copolymer composition distribution. Doping AlCl₃ in the catalyst, changing cocatalyst and adding external donor mainly changed the weight ratio of fraction A to fraction C, but exerted little influences on their composition. According to the sequence distribution data of the fractions, doping AlCl₃ in the catalyst resulted in slight decrease of product of reactivity ratios (r₁r₂) in both fraction A and fraction C.     

Microwave-assisted methylation of phenols with tetramethylammonium chloride in the presence of K2CO3 or Cs2CO3

We have evaluated the potential of using tetramethylammonium chloride (Me₄NCl) as an alternative methylating agent for phenols under microwave-assisted conditions. Its chemical behavior was tested in a reaction with 2-naphthol in the presence of various bases and solvents. The method was then applied in 1,2-dimethoxyethane or toluene under heterogeneous conditions for the O-methylation of a series of phenolic compounds. We found that many simple phenols can be methylated in the presence of K₂CO₃, whereas some other less-reactive phenols require the presence of the more reactive Cs₂CO₃.     

Interaction of methanol with hydrogen sulfide in the presence of K2WO4/Al2O3

Kinetic data show that in the presence of K₂WO₄/Al₂O₃, methanethiol is largely produced by the reaction of H₂S with metanol and partly with dimethyl ether. Dimethyl sulfide is formed during the interaction of methanethiol with methanol, of H₂S with dimethyl ether and as a result of methanethiol disproportionation. Methane and carbon oxides are the decomposition products of methanethiol and dimethyl sulfide and of methanol and dimethyl ether, respectively.

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, K₂WO₄/Al₂O₃ H₂S — . , H₂S . , — .

     

Gas phase electron diffraction study of SiH3N3 and (SiH3)2 NCN

The molecular structures of SiH₃N₃ and (SiH₃)₂ NCN have been determined by electron diffraction : SiH₃N₃ has a non-linear SiN₃ skeleton, and (SiH₃)₂ NCN is a carbodiimide with SiNCN Si probably linear. A new model is proposed which rationalises the observed geometry of a number of molecular pseudohalides.     

Fluoroferric hexafluorosilicates obtained in the reaction of Fe(OH)3 with H2SiF6 and in the oxidation of FeSiF6 with H2O2

The title reactions were found to proceed in solution with formation of a mixture of the complexes (FeF)SiF₆ and (FeF₂)₂SiF₆ with an average atomic ratio F/Fe ? 1.6. Partial reactions involved in equilibria in the reaction system are proposed and discussed.     

Kinetics of ethylene oxidation to EGMA in the presence of PdCl2 and Fe(NO3)3

Kinetic regularities of ethylene oxidation to ethylene glycol monoacetate (EGMA) in the presence of a PdCl₂ and Fe(NO₃)₃-containing catalytic system has been studied to clarify the peculiarities of the mechanism of this reaction.

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Magnetic poly(glycidyl methacrylate)-based microspheres prepared by suspension polymerization in the presence of modified La0.75Sr0.25MnO3 nanoparticles

With the aim of preparing new magnetic poly(glycidyl methacrylate) (PGMA) microspheres suitable for magnetic separation, La_0.75Sr_0.25MnO₃ nanoparticles were selected as a core material. In order to improve their compatibility with PGMA, the surface of the nanoparticles was treated with penta(methylethylene glycol) phosphate methacrylate (PMGPMA) as a stabilizer. Subsequently, the nanoparticles were encapsulated by the suspension polymerization of glycidyl methacrylate (GMA) resulting in a relatively homogeneous distribution of La_0.75Sr_0.25MnO₃ nanoparticle aggregates inside the polymer microspheres. Microspheres in the size range of a hundred micrometers with a broad particle size distribution were obtained. PMGPMA can be considered to be an efficient compatibilizer between La_0.75Sr_0.25MnO₃ nanoparticles and PGMA. Both PMGPMA-coated La_0.75Sr_0.25MnO₃ nanoparticles and magnetic PGMA microspheres were characterized in terms of morphology, particle size, composition and magnetic properties by the appropriate methods, such as X-ray diffraction, FTIR spectroscopy, thermogravimetric analysis (TGA), transmission electron microscopy (TEM), light microscopy and SQUID magnetometry.     

CO oxidation over CuCr/Al2O3 catalysts in presence of SO2

Poisoning of variously prepared CuCr/Al₂O₃ catalysts having different compositions by sulfur dioxide has been studied. Comparative values for a decrease in the catalyst activities have been obtained.

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CO .

     

Synthesis of cyclic polysulfides by the reaction of trimethylvinylsilane with S8 in the presence of Fe3(CO)12

Reaction of trimethylvinylsilane with S₈ in the presence of Fe₃(CO)₁₂ yielded the following compounds: S₂Fe₂(CO)₆, S₂Fe₃(CO)₉, 1-trimethylsilyl-2,3,4,5,6-pentathiacycloheptane, 1,4-di(trimethylsilyl)-2,3,6-trithiacycloheptane, 1,4-di(trimethylsilyl)-2,3,6,7-tetrathiacyclooctane. An X-ray analysis was performed for the two latter polysulfides.     

Cationic polymerization of isobutylene with H2O/TiCl4 initiating system in the presence of electron pair donors

Cationic polymerization of isobutylene (IB) in a mixture of methylene dichloride (CH₂Cl₂) and n-hexane (n-Hex) was conducted by using H₂O as initiator, TiCl₄ as co-initiator in the presence of strong external electron pair donor (ED), such as pyridine (Py), dimethylacetamide (DMA) or triethylamine (TEA). The effects of ED concentration, TiCl₄ concentration, solvent polarity, polymerization temperature (T) and time on IB polymerization, molecular weight (MW) and molecular weight distribution (MWD, M_w/M_n) of polyisobutylene (PIB) products were investigated. The relative amount of polymer formed via uncontrolled initiation by conventional active species (I) decreased with increasing the solvent polarity, TiCl₄ concentration and ED concentration in the polymerization. The desirable polymerization of IB with apparent absence of chain transfer reactions could be obtained by H₂O/TiCl₄ initiating system in the presence of ED under the appropriate reaction conditions. The external electron pair donors and TiCl₄ did specially play important and effective roles on polymerization.     

The gas-phase molecular structure of CF3HgCH3 - an electron diffraction and microwave study

The molecular structure of CF₃HgCH₃ in the gas phase is determined by a joint analysis of electron diffraction and microwave data. The following geometric parameters (r_av values) are derived: r(Hg—CH₃) = 2.052(5) Å, r(Hg—CF₃) = 2.116(4) Å. r(C-F) = 1.354(2) Å. r(C—H) = 1.079(14) Å, ∠.FCF = 105.7(0.2)° and ∠HCH = 107.0(1.5)°. Error limits are twice the standard deviations.     

Ionization of NF3 by electron impact

The ionization and dissociative ionization of NF₃ by electron impact has been measured by Fourier transform mass spectrometry (FTMS). The total ionization cross-section rises to a maximum value of 2.4±0.4×10⁻¹⁶ cm² at 140 eV. Estimates of the total single ionization cross-section using ab initio energies with the binary encounter Bethe (BEB) [Y.K. Kim, M.E. Rudd, Phys. Rev. A 50 (1994) 3594] or Deutsch–Märk [Int. J. Mass Spec. 197 (2000) 37] models are roughly twice the measured values. The partial cross-sections creating NF_x⁺ (x=0, 1, 2, 3), F⁺, and NF_x²⁺ (x=1, 2, 3) are reported. Differences between the FTMS results and quadrupole data and fast atom beam results of Tarnovsky et al. [Int. J. Mass Spectrom. Ion Processes 133 (1994) 175] are discussed.     

L3/L2 white-line intensity ratios in the electron energy-loss spectra of 3d transition-metal oxides

The L₃/L₂ white-line intensity ratio in transition-metal oxides deviates widely from the statistical value of 2 : 1 but shows interesting systematics. In a series of oxides of a given metal, the ratio reaches a maximum for the d⁵ configuration (e.g. MnO) and a minimum for the d⁰ configuration (e.g. KMnO₄). In a series of monoxides, sesquioxides and dioxides of different metals, the ratio is again a maximum at the d⁵ configuration and decreases as the configuration changes towards d⁰ or d¹⁰. Our results, obtained by electron energy-loss spectroscopy, carried out in an electron microscope, are interpreted on an atomic mechanism involving spin-spin coupling. According to this model, the L₂ transition probability decreases in the progression d⁰ to d⁵ whereas the L₃ transition probability decreases beyond d⁵.     

Epoxidation with molecular oxygen in the presence of PdCl (NO2) (CH3CN)2

Several mono or non conjugated diolefins are submitted to the action of oxygen in presence of catalytic amounts of PdCl (NO₂) (CH₃CN)₂. Depending on the olefin structures methylketones or epoxides are obtained.     

Reverse atom transfer radical polymerization of methyl methacrylate with FeCl3/pyromellitic acid

Iron^III chloride coordinated by pyromellitic acid was successfully used as the catalytic system in reverse atom transfer radical polymerization of MMA. Well-defined poly(methyl methacrylate) with narrow molecular weight distribution was synthesized in N,N-dimethylformamide at 80-110 °C. Chain extension was performed to confirm the living nature of the polymer. The presence of the end chloride atom on the resulting PMMA was demonstrated by ¹HNMR spectroscopy. This catalyst system is effective for reverse ATRP of methacrylates but not for acrylates.