The synthesis and vibrational spectra of the antimony(V)fluoride-fluorosulfates SbF3(SO3F)2, SbF4(SO3F) and Sb2F9(SO3F)

The synthesis of the title compounds by a variety of routes is described. These routes involve the oxidation of antimony(III)fluoride by bis(fluorosulfuryl)peroxide and the use of non-statistical ligand redistribution reactions. Complex formation with ClO₂SO₃F leads to ClO₂[SbF_n(SO₃F)_6-n], with n=3 or 4. Polarized Raman data and low temperature infrared data are reported. All antimony(V)fluoride-fluorosulfates are found to have fluorosulfate bridges with SbF₃(SO₃F)₂ and SbF₄(SO₃F) being polymers. Ionic formulations for the ClO⁺₂ complexes are again based on vibrational spectra.     

Synthesis, F,Te NMR Spectra and crystal structure of NBu4TeF5 and NH4TeF5 (NH4F)0.25 (‘(NH4)2TeF6’)

¹⁹F and ¹²⁵Te NMR in different organic solvents and X-Ray investigations NBu₄TeF₅ (I) and ‘(NH₄)₂TeF₆’ (II) show that TeF₅⁻ anion in (I) both solution and the solid state has a square pyramidal structure. No octahedral arrangement of fluorine was found in (II). This compound consists of NH₄TeF₅ and NH₄F molecules, the NH₄F being in channels between the layers of NH₄TeF₅.     

Vibrational study of hydrogen bonding and structural disorder in Na2H(SO4)2, K3H(SO4)2 and (NH4)3H(SO4)2 crystals

Infrared and Raman spectra on Na₃H(SO₄)₂, K₃ H(SO₄)₂ and (NH₄)₃ H(SO₄)₂ crystals have been investigated at 300 and 100 K in the 4000 to 30 cm⁻¹ region. An assignment of bands in terms of OH group frequencies and more or less distorted tetrahedra of ammonium and sulphate ions is given. The crystallographic and spectroscopic symmetry and/or dissymetry of OHO hydrogen bonds linking sulphate ions into dimers is discussed using OH group frequencies and the splitting of the v₁ (SO₄) Raman bands as criteria. In the particular case of (NH₄)₃H(SO₄)₁ compound containing several solid phases it can be shown that the room temperature phase (II) is strongly disordered, principally because of an orientational disorder of ammonium ions, and that a progressive ordering takes place with temperature lowering.     

Spectroscopic properties of guanidinium zinc sulphate [C(NH2)3]2Zn(SO4)2 and ab initio calculations of [C(NH2)3]2 and HC(NH2)3

Raman and FTIR spectra of guanidinium zinc sulphate [C(NH₂)₃]₂Zn(SO₄)₂ are recorded and the spectral bands assignment is carried out in terms of the fundamental modes of vibration of the guanidinium cations and sulphate anions. The analysis of the spectrum reveals distorted SO₄²⁻ tetrahedra with distinct S–O bonds. The distortion of the sulphate tetrahedra is attributed to Zn–O–S–O–Zn bridging in the structure as well as hydrogen bonding. The CN₃ group is planar which is expressed in the twofold symmetry along the C–N (1) vector. Spectral studies also reveal the presence of hydrogen bonds in the sample. The vibrational frequencies of [C(NH₂)₃]₂ and HC(NH₂)₃ are computed using Gaussian 03 with HF/6-31G* as basis set.     

Investigation of phase equilibria in the systems K2SO4Sc2(SO4)3, Rb2SO4Sc2(SO4)3 and Cs2SO4Sc2(SO4)3

Phase diagrams of the systems K₂SO₄Sc₂(SO₄)₃, Rb₂SO ₄Sc₂(SO₄)₃ and Cs₂SO₄ Sc₂(SO₄)₃ have been investigated by X-ray diffraction phase analysis and differential thermal analysis techniques. A salient feature of all the systems is the formation of M₃Sc(SO₄)₃, which melt incongruently, and MSc(SO₄)₂, which on heating decompose in the solid state.     

原位产生的SO42-配位的二维无机钴配合物K2[Co3(OH)2(SO4)3(H2O)2]的水热合成及晶体结构

相同的水热反应条件下4-氨基-二(2-吡啶基)-1，2，4-三氮唑(abpt)、KSCN与钴盐(CoCl₂·6H₂O)反应合成了2种新的钴配合物:零维的单核配合物[CoSCN(abpt)] (1α)和二维的无机层状配合物K₂[Co₃(OH)₂(SO₄)₃(H₂O)₂] (1β)，并通过元素分析和红外光谱对其进行了表征。配合物1α的晶体属于单斜晶系，P2₁/c空间群。配合物1β晶体属于正交晶系，Cmc2₁空间群。在配合物1α中，abpt和SCN^-配体都参与配位与Co(Ⅱ)离子形成了2个不同的单核单元，这些单核单元又通过S原子和N原子之间的氢键作用连成了三维超分子结构;在配合物1β中，abpt配体没有参与配位，而SCN^-配体则被氧化成了SO₄^2-离子并与Co(Ⅱ)离子配位形成了二维配位层状结构，相邻层之间进一步通过氢键作用形成了沿c轴方向有孔道的三维超分子网络，这些孔道里面填充着反离子K+。     

Preparation and chemistry of cis- and trans- F4Te(OH)2

Trans-tetrafluoro-orthotelluric acid (mp. 118°) is formed from orthotelluric acid and aqueous HF. Cis-tetrafluoro-orthotelluric acid (mp. 160°) is the only product of the hydrolysis of pentafluoro-orthotelluric acid. With the above compounds as starting materials the stereochemistry of the hydrolysis of TeF₆ can be followed up closely. Interaction of cis- and trans-F₄Te(OH)₂ with CH₂N₂ leads to cis- and trans-F₄Te(OCH₃)₂ and cis- and trans-CH₃OTeF₂OH. Differences in chemical reactivity of these compounds are presented.     

Fe2(SO4)3/γ-Al2O3固体超强酸的Mössbauer谱研究

采用浸渍法制备了一系列Fe2(SO4)3/ γ-Al2O3型固体超强酸样品,用Moessbauer谱和XRD研究了不同温度处理对样品中铁组分的存在状态及稳定性的影响。结果表明,随Fe2(SO4)3含量的变化,铁组分可以在γ-Al2O3表面以单层分散和无定形形式存在;当温度≥600℃时,无定形状态的Fe2(SO4)3又生成晶态的Fe2(SO4)3,而形成的晶态Fe2(SO4)3即使在700℃时也不分解。     

Tieftemperatur-flüssigphase-fluorierung von (C6F5)2Te: Bildung von (C6F5)2TeF2, (C6F5)2TeF4 und (C6F11)2TeF4 [1]

(C₆F₅)₂Te reacts with elemental fluorine step by step to form the tellurium fluorides (C₆F₅)₂TeF₂, (C₆F₅)₂TeF₄ and (C₆F₁₁)₂TeF₄, which can be isolated in pure states. The intermediates (C₆F_11?2n)₂TeF₄ (n = 1,2) are detected spectroscopically. (C₆F₅)₂TeF₂ is also formed from the reaction of (C₆F₅)₂Te with XeF₂. The preparations, properties and ¹⁹F n.m.r. spectra of these new compounds are discussed, the mass and vibrational spectra are described.     

Infrared spectra of KNaSO4 and K3Na(SO4)2

The infrared spectra, transmittance and polarized reflectance, of KNaSO₄ and K₃Na(SO₄)₂ are reported. Group theoretical analysis was carried out and a vibrational assignment proposed on basis of C_3v and D_3d symmetries. Factor group and site effects are discussed.     

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.     

Synthesis of Cr2(MoO4)3

Studies on the kinetics and mechanism of the reaction leading to Cr₂(MoO₄)₃ have been made using X-ray diffraction and infrared spectroscopy. The apparent activation energy, E=285±22 kJ/mol has been calculated, based on the Ginstling-Brounstein diffusion controlled model.     

Synthesis and crystal chemistry of NH3(MoO3)3

NH₃(MoO₃)₃ crystallizes with hexagonal symmetry, space group $\text{P6}{}_3\text{m}$, lattice constants a = 10.568 Å, c = 3.726 Å, and Z = 2. The crystal structure has been determined by Patterson synthesis and refined assuming isotropic temperature factors to a final conventional R value of 0.085. The structure shows a three-dimensional arrangement built up of double chains of distorted MoO₆ octahedra, parallel to the [001] direction. The octahedral double chains are linked among each other through common oxygen atoms. In addition to the shared oxygen atoms, each molybdenum is coordinated to one terminal oxygen. MoO distances range from 1.645 to 2.378 Å and OMoO angles from 74.3 to 114.3°. These results are consistent with the fact that molybdenum in high-valence states shows octahedral coordination with terminal oxygens.     

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.     

Proton dynamics in superionic phase of Tl3H(SO4)2

Electrical properties and ¹H-NMR absorption line have been measured, in order to investigate proton dynamics in a superionic phase in Tl₃H(SO₄)₂. From the measurement of the thermoelectric power, it is found that a majority carrier in electrical conductivity is a proton. Moreover, from ¹H-NMR measurement it is also found that the activation energy 0.33 eV of the hopping motion of protons is close to 0.38 eV as observed in the electrical conductivity measurement. These results indicate that the electrical conductivity in the superionic phase is caused by the hopping motion of protons accompanied by the breaking of the hydrogen bonds.     

PbMn(SO4)2: A new chiral antiferromagnet

PbMn(SO₄)₂ has been synthesized in an evacuated quartz tube. The nuclear and magnetic crystal structures have been determined using powder X-ray and neutron diffraction. This material crystallizes in the enantiomorphic space group pair P4₁2₁2(92) and P4₃2₁2(96), forming a double-helical arrangement of Pb²⁺ and Mn²⁺ cations. The Mn²⁺O₆ octahedra are distorted. Each 3d⁵ Mn²⁺ has four nearest-neighbors and four next-nearest-neighbors adopting a frustrating arrangement. The compound orders antiferromagnetically at 5.5 K. Field dependent specific heat and magnetization measurements show that T_N is suppressed to 3.3 K when μ₀H=9 T.