Ab initio investigation of the potential energy surfaces of C2H2F2 and C2H2F2+

Ab initio MO calculations have been performed for neutral and cationic C₂H₂F₂ structures. Olefinic and carbene structures are investigated for the neutral isomers, while olefinic, carbene, and fluoronium-type cations are found. Stability orders and rotational barriers are discussed in terms of orbital and Coulomb interaction. Contrary to previous studies, the higher stability of the geminal isomers is interpreted to be caused by Coulomb attraction.     

On the studies of the vibrational spectra of cluster [Mo2O2S2(S2)2]2-

IR and Raman spectra of [Mo₂O₂S₂(S₂)₂]^2- were reported. The resonance Raman spectra and the depolarization ratios in CH₃CN solution were measured. By using the data of crystal structure, the simplified normal coordinate calculation of the stretching vibrations for anion [Mo₂O₂S₂(S₂)₂]^2- was performed. The results obtained are useful to assign the vibrational bands of some Mo-Fe-S clusters.     

Electrochemical study of (NEt4)2Cl2FeS2MoS2 and (NEt4)2Cl2FeS2MoS2FeCl2

Summary The ability of [MoS₄]^2–, anions to be used as ligands for transition metal ions has been widely demonstrated, especially with Fe²⁺. The present study has been restricted to linear complexes such as (NEt₄)₂ [Cl₂FeS₂MoS₂] and (NEt₄)₂[Cl₂FeS₂MoS₂FeCl₂]. Their electrochemical properties are described: upon electrochemical reduction, these compounds yield MoS₂, as a black precipitate, and an iron complex in solution, assumed to be [SFeCl₂]^2–. The electrochemical reduction goes through two electron transfers, coupled with the breakdown of the molecular skeleton: a DISPl and an ECE mechanism. Depending on the solvent, the following equilibrium may be observed: [Cl₄Fe₂MoS₄]^2–[Cl₂FeMoS₄]^2–+FeCl₂. The equilibrium constant, K_D, was evaluated by differential pulse polarography. K_D is tightly related to the donor number of the solvent.     

Syntheses,Crystal Structure,and Properties of Hf2Ni2In,Hf2Ni2Sn,Hf2Cu2In,and Hf2Pd2In with Ordered Zr3Al2 Type Structure

Hf₂Ni₂In, Hf₂Ni₂Sn, Hf₂Cu₂In, and Hf₂Pd₂In were synthesized by reacting the elements in an arc-melting furnace under argon and subsequent annealing at 970 K. They crystallize with an ordered Zr₃Al₂ type structure, space group P4₂/mnm which was refined from single crystal X-ray data for Hf₂Ni₂In (a = 713.9(1) pm, c = 660.4(2) pm, wR2 = 0.0665, 513 F² values) and Hf₂Ni₂Sn (a = 703.1(1) pm, c = 676.1(2) pm, wR2 = 0.0423, 507 F² values) with 18 parameters for each refinement. The lattice constants for Hf₂Cu₂In and Hf₂Pd₂In are a = 715.5(1) pm, c = 677.0(1) pm and a = 742.6(1) pm, c = 679.4(2) pm, respectively. The structures may be considered as an intergrowth of distorted CsCl- and AlB₂-like slabs. Magnetic susceptibility measurements indicate Pauli paramagnetism for Hf₂Ni₂In and Hf₂Ni₂Sn, which is consistent with the metallic conductivity observed for Hf₂Ni₂In. ¹¹⁹Sn Mössbauer spectroscopy of Hf₂Ni₂Sn shows one signal with an isomer shift of δ = 1.59(1) mm/s subjected to quadrupole splitting of δE_q = 0.81(1) mm/s.     

Synthesis and crystal structure of [Nb2(S1.72Se2.28)(S2CNEt2)4]—A solid solution based on [Nb2(μ2, η2-X2)2(S2CNEt2)4], where X2=S2, SSe,and Se2. New model of structure refinement of [Nb2(S2)2(S2CNEt2)4], where X2=S2, SSe,and Se2. New model of structure refinement of [Nb2(S2)2(S2CNEt2)4]

The crystal structure of [Nb₂(S_1.72Se_2.28)(S₂CNEt₂)₄], which is a solid solution based on [Nb₂(μ₂, η²-X₂)₂(S₂CNEt₂)₄], where X₂=S₂, SSe, and Se₂, is determined. The compound was obtained by the reaction of NaS₂CNEt₂ in CH₃CN with the product of the reaction of the NbSe₂Cl₂-KNCS fusion cake with an aqueous solution of Bu₄NBr (yield 30%). The crystals are monoclinic, a=21.319(11), b=7.008(1), c=16.673(8) Å, β=133.99(2)°, V_cell=1792(1) ų, space group C2/m, Z=2, d_calc=1.879 g/cm³ for C₂₀H₄₀N₄Nb₂S_9.72Se_2.28, Syntex P2₁, λCukα, N_meas/corr=2423/1191, R(F)=0.0569 and wR(F²)=0.1282 for 889 F_hkl>4σ(F). The compound is isostructural to the thio analog Nb₂S₄(S₂CNEt₂)₄ studied earlier; in both cases, the molecule is disordered in crystals over two positions. The composition was refined by diffraction data. The results are in good agreement with the Raman and FMB (fast molecule bombardment) mass spectrometry data. The structure of Nb₂S₄(S₂CNEt₂)₄ was refined for the second time using a new model of disorder; as a result of the refinement, a normal value of S?S bond length in the S₂ ligand [2.027(5) Å] was obtained.     

The non-covalent bindings of CF2Cl2 with NO and SO2

Ab initio calculations have been performed on the complexes of CF₂Cl₂ with NO and SO₂, and a set of stable configurations for CF₂Cl₂–NO and CF₂Cl₂–SO₂ were found with no imaginary frequencies by the MP2 method. In addition, the binding energy and the NBO analysis were used to evaluate the relative stability of the complexes. The calculated results indicate that the weak interactions in the CF₂Cl₂–NO and CF₂Cl₂–SO₂ systems involved are enhanced with the increase of the number of non-covalent bonds. Further studies predict that the CF₂Cl₂–SO₂ system may play a more important role than the CF₂Cl₂–NO system in environmental problem because the former offers a stronger interaction than the latter. Furthermore, the non-covalent binding interactions of Cl···N and Cl···O for CF₂Cl₂–NO system, Cl···O, Cl···S and F···S for CF₂Cl₂–SO₂ system, are the dominant forces, which seem to be very significant as a driving force influencing the arrangement of molecules, especially in CF₂Cl₂–SO₂ system.     

Crystal Structures of [Bu2Sn(O2PPh2)2], [Ph2Sn(O2PPh2)2], and [PhClSn(O2PPh2)OMe]2. Raman Spectra of [Ph2Sn(O2PPh2)2] and [PhClSn(O2PPh2)OMe]2

[(n‐Bu)₂Sn(O₂PPh₂)₂] ( 1 ), and [Ph₂Sn(O₂PPh₂)₂] ( 2 ) have been synthesized by the reactions of R₂SnCl₂ (R=n‐Bu, Ph) with HO₂PPh₂ in Methanol. From the reaction of Ph₂SnCl₂ with diphenylphosphinic acid a third product [PhClSn(O₂PPh₂)OMe]₂ ( 3 ) could be isolated. X‐ray diffraction studies show 1 to crystallize in the monoclinic space group P2₁/c with a = 1303.7(1) pm, b = 2286.9(2) pm, c = 1063.1(1) pm, β = 94.383(6)°, and Z = 4. 2 crystallizes triclinic in the space group , the cell parameters being a = 1293.2(2) pm, b = 1478.5(4) pm, c = 1507.2(3) pm, α = 98.86(3)°, β = 109.63(2)°, γ = 114.88(2)°, and Z = 2. Both compounds form arrays of eight‐membered rings (SnOPO)₂ linked at the tin atoms to form chains of infinite length. The dimer 3 consists of a like ring, in which the tin atoms are bridged by methoxo groups. It crystallizes triclinic in space group with a = 946.4(1) pm, b = 963.7(1) pm, c = 1174.2(1) pm, α = 82.495(6)°, β = 66.451(6)°, γ = 74.922(6)°, and Z = 1 for the dimer. The Raman spectra of 2 and 3 are given and discussed.     

Ab initio studies of internal rotation barriers and vibrational frequencies of (C2H2)2, (CO2)2, and C2H2-CO2

We have performed large-scaleab initio calculations using second order Møller-Plesset perturbation theory (MP2) on the three van der Waals dimers formed from acetylene and carbon dioxide. Intermolecular geometrical parameters are reliably computed at this level of theory. Calculations of vibrational frequencies of the van der Waals modes, currently unobtainable by experimental means, give important information about the intermolecular potential and predict significant large-amplitude motion. Zero point energy contributions are shown to be vital in assessing the relative stability of conformations which are close in energy. Our studies suggest that the barrier to interconversion tunnelling in (CO₂)₂ is significantly smaller than previously inferred and is approximately the same as in (C₂H₂)₂. The reason for the rigidity of (CO₂)₂ is the difference in monomer centre-of-mass separation between ground state and transition state. We also show that, in addition to the previously observedC _2v form, the collinear form of C₂H₂-CO₂ is a local minimum on its potential energy surface.     

Darstellung und Kristallstruktur der Pnictidoxide Na2Ti2As2O und Na2Ti2Sb2O

Preparation and Crystal Structure of the Pnictide Oxides Na₂Ti₂As₂O and Na₂Ti₂Sb₂O Na₂Ti₂As₂O and Na₂Ti₂Sb₂O were synthesized in form of very easily hydrolysed metallic-grey powders by reaction of Na₂O and TiAs resp. TiSb in sealed tantalum tubes under argon. The tetrahedral bodycentered crystallizing compounds from a modified anti-K₂NiF₄ structure type [1] (also called Eu₄As₂O-type [2,3]), space group I4/mmm (no. 139), with the lattice constants for Na₂Ti₂As₂O: a = 407.0(2) pm, c = 1528.8(4) pm and for Na₂Ti₂Sb₂O: a = 414.4(0) pm, c = 1656.1(1) pm. Magnetic measurements of powder samples of Na₂Ti₂Sb₂O show antiferromagnetic interaction within the Ti—O-layers. Superconductivity was not found by ac-shielding method down to 4 K.     

Homopolymerization of 2-alkyl- and 2-aryl-2-oxazolines

2-Aryl- and 2-alkyl-2-oxazolines have been polymerized to poly-(N-aroyl)aziridines and poly(N-acyl)aziridines, respectively, in the presence of boron trifluoride. The polymers obtained were glassy, light yellow resins with molecular weights ranging from 3500 to 7500 (35–50 oxazoline units per chain). The polymerization rates have been determined for several of these monomers. A polymerization mechanism is proposed.     

Investigation of peroxyhydrates and hydrates of rubidium and cesium carbonates Communication 2. Physicochemical study of the ternary system Rb2CO2-H2O2-H2O

Conclusions A physicochemical investigation of the system Rb₂CO₃-H₂O₂-H₂O in the region of high hydrogen peroxide concentrations at low temperatures revealed for the first time the formation of a peroxyhydrate with a high hydrogen peroxide content, of the composition Rb₂CO₃ · 6H₂O₂.     

Redetermination of NaGdS2, NaLuS2 and NaYS2

The title structures NaGdS₂ (sodium gadolinium sulfide), NaLuS₂ (sodium lutetium sulfide) and NaYS₂ (sodium yttrium sulfide) were redetermined in order to improve the structural information available for the family of group 1 and thallium rare earth sulfides, which are isostructural with the rhombohedral α‐NaFeO₂ structure type. In particular, the present investigation has been directed at the rhombohedral sodium rare earth sulfides. The observed dependence of the fractional coordinate z(S²⁻) on the identity of the rare earth element in the newly determined structures is in agreement with the known structures of the potassium and rubidium analogues. Crystals of NaGdS₂ and NaLuS₂ display obverse–reverse twinning.     

Mechanism and kinetics of glass-ceramics formation in the LiO2-SiO2-CaO-P2O5-CaF2 system

Two glasses based on lithium disilicate (LS₂), with and without fluorapatite (FA), were synthesised in the Li₂O-SiO₂-CaO-P₂O₅-CaF₂ system with P₂O₅: CaO: CaF₂ ratios corresponding to fluorapatite. Glass-ceramics have then been prepared by thermal treatment. The mechanism and kinetics of crystallization as functions of grain size and rate of heating were investigated using thermal analysis methods. The smaller particles crystallize preferentially by surface crystallization, which is replaced by volume crystallization at larger particle sizes. Inclusion of FA in the LS₂ favours crystallization through the surface mechanism. The onset limit for volume crystallization replacing the surface mechanism is at about 0.3 mm for pure LS₂ glass and 0.9 mm for glass containing FA. The calculated activation energies of the glasses (₂99 ± 1 kJ mol-1 for pure LS₂ glass and ₂88 ± 7 kJ mol⁻¹ for glass containing FA according to Kissinger, or 313 ± 1 kJ mol-1 for pure LS₂ glass and 303 ± 8 kJ mol-1 for glass containing FA according to Ozawa) indicate that the tendency of the glasses to crystallize is supported by the FA presence. Bioactivity of all samples has been proved in vitro by the formation of new layers of apatite-like phases after soaking in SBF.      

Rates of reaction of atomic oxygen with C2H3F,C2H3Cl,C2H3Br, 1,1-C2H2F2, and 1,2-C2H2F2

Rate constants for the reactions of atomic oxygen (O³P) with C₂H₃F, C₂H₃Cl, C₂H₃Br, 1,1-C₂H₂F₂, and 1,2-C₂H₂F₂ have been measured at 307°K using a discharge-flow system coupled to a mass spectrometer. The rate constants for these reactions are (in units of 10¹¹ cm³ mole^?1 s^?1) 2.63 ± 0.38, 5.22 ± 0.24, 4.90 ± 0.34, 2.19 ± 0.18, and 2.70 ± 0.34, respectively. For some of these reactions, the product carbonyl halides were identified.     

Construction of 2D-2D TiO2 nanosheet/layered WS2 heterojunctions with enhanced visible-light-responsive photocatalytic activity

Constructing nanocomposites that combine the advantages of composite materials, nanomaterials, and interfaces has been regarded as an important strategy to improve the photocatalytic activity of TiO₂. In this study, 2D-2D TiO₂ nanosheet/layered WS₂ (TNS/WS₂) heterojunctions were prepared via a hydrothermal method. The structure and morphology of the photocatalysts were systematically characterized. Layered WS₂ (～4 layers) was wrapped on the surface of TiO₂ nanosheets with a plate-to-plate stacked structure and connected with each other by W=O bonds. The as-prepared TNS/WS₂ heterojunctions showed higher photocatalytic activity for the degradation of RhB under visible-light irradiation, than pristine TiO₂ nanosheets and layered WS₂. The improvement of photocatalytic activity was primarily attributed to enhanced charge separation efficiency, which originated from the perfect 2D-2D nanointerfaces and intimate interfacial contacts between TiO₂ nanosheets and layered WS₂. Based on experimental results, a double-transfer photocatalytic mechanism for the TNS/WS₂ heterojunctions was proposed and discussed. This work provides new insights for synthesizing highly efficient and environmentally stable photocatalysts by engineering the surface heterojunctions.     

Direct Synthesis of H2O2 by a H2/O2 Fuel Cell

Direct synthesis of H₂O₂ solutions by a fuel cell method was reviewed. The fuel cell reactor of [O₂, gas-diffusion cathode electrolyte solutions Nafion membrane electrolyte solutions gas-diffusion anode, H₂] is very effective for formation of H₂O₂. The three-phase boundary (O₂(g)–electrode(s)–electrolyte(l)) in the gas-diffusion cathode is essential for efficient formation of H₂O₂. Fast diffusion processes of O₂ to the active surface and of H₂O₂ to the bulk electrolyte solutions are essential for H₂O₂ accumulation. The maxima H₂O₂ concentrations of 1.2 M (3.5 wt%) and 2.4 M (7.0 wt%) were accomplished by the heat-treated Mn-OEP/AC electrocatalyst with H₂SO₄ electrolyte and by the VGCF electrocatalyst with NaOH electrolyte, respectively, under short circuit conditions.     

DSC study of the kinetics of the thermal dehydration of BaCl2 · 2H2O and BaCl2 · H2O

The kinetics of the thermal dehydration of various kinds of BaCl₂ · 2H₂O and of BaCl₂ · H₂O are investigated using a differential scanning calorimeter. The loss of H₂O proceeds in two steps: BaCl₂ · 2H₂O→BaCl₂ · H₂O→BaCl₂ and is therefore revealed by two endothermic peaks. In the experiments at varying temperature both steps follow a contracting-circle law, after an initial acceleratory stage according to a (n=2) power law. In the experiments at constant temperature, after an initial acceleratory stage according to a (n=2) power law, both steps (except BaCl₂ · 2H₂O single-crystals which follow a contracting-circle law) follow an Avrami-Erofeev law (withn=2) in the form used by Galwey and Jacobs. The activation energies for the various steps are compared and the different kinetic behaviour is discussed.     

Structural chemistry of Ba2CdS3, Ba2CdSe3, BaCdS2, BaCu2S2 and BaCu2Se2

The structures of all compounds were determined from three dimensional single crystal X-ray diffraction data and refined by least squares. Ba₂CdS₃ and Ba₂CdSe₃ are isostructural, Pnma, a = 8.9145(6)Å, b = 4.3356(2)Å, c = 17.2439(9)Å for the former compound and a = 9.2247Å, b = 4,4823(6)Å, c = 17.8706(11)Å for the latter, z = 4, R = 0.0751 and R = 0.0462, respectively. The compounds are isostructural with the previously reported Mn analogues and with K₂AgI₃. Cd ions are in tetrahedral environment and the tetrahedra form infinite linear chains by corner sharing. Ba ions are in 7-fold coordination in which 6 anions form a trigonal prism and 1 anion caps one of the rectangular faces. BaCdS₂, Pnma, a = 7.2781(3)Å, b = 4.1670(1)Å, c = 13.9189(6)Å, z = 4, R = 0.0685. Cd ions can be considered to have a triangular planar coordination with CdS distances of 2.47 and 2.53 Å (twice). Two additional S ions are at 2.89 and 3.22 Å to complete a triangular bipyramidal configuration. Ba is in 7-fold coordination with the anions forming a trigonal prism which is capped on one rectangular face. The compound is isostructural with BaCdO₂ and is related to the structure of BaMnS₂. BaCdSe₂ could not be prepared. BaCu₂S₂ and BaCu₂Se₂ are isostructural, Pnma, a = 9.3081(4)Å, b = 4.0612(3)Å, c = 10.4084(5)Å for the sulfide and a = 9.5944(6)Å, b = 4.2142(4)Å, c = 10.7748(8)Å for the selenide, z = 4, R = 0.0634 and 0.0373, respectively. Ba ions are in the usual 7-fold, capped hexagonal prism, coordination. However, 9 Cu ions also can be considered to form a trigonal prism with all rectangular faces capped, around Ba since the BaCu distances range from 3.24 to 3.54 Å for the sulfide and from 3.37 to 3.67 Å for the selenide. One of the Cu ions is in a very distorted tetrahedral environment and the second one is located in a more regular tetrahedral configuration of the anions. Two independent infinite chains of tetrahedra are present. They are formed by sharing of two adjacent edges of each tetrahedron and then these chains in turn are linked by corner sharing into a three-dimensional network of tetrahedra.     

Mode Selective Stereomutation and Parity Violation in Disulfane Isotopomers H2S2, D2S2, T2S2

We report quantitative calculations of stereomutation tunneling in the disulfane isotopomers H₂S₂, D₂S₂, and T₂S₂, which are chiral in their equilibrium geometry. The quasi‐adiabatic channel, quasi‐harmonic reaction path Hamiltonian approach used here treats stereomutation including all internal degrees of freedom. The torsional motion is handled as an anharmonic reaction coordinate in detail, whereas all the remaining degrees of freedom are taken into account approximately. We predict how stereomutation is catalyzed or inhibited by excitation of the various vibrational modes. The agreement of our theoretical results with spectroscopic data from the literature on H₂S₂ and D₂S₂ is excellent. We furthermore predict the influence of parity violation on stereomutation as characterized approximately by the ratio (ΔE_pv/ΔE_±) of the (local or vibrationally averaged) parity violating potential ΔE_pv and the tunneling splittings ΔE_± in the symmetrical case. This ratio is exceedingly small for the reference molecules H₂O₂ and D₂O₂, and still very small (2⋅10⁻⁶ cm⁻¹) for H₂S₂, which, thus, all exhibit essentially parity conservation in the dynamics. However, for D₂S₂ it is ca. 0.002, and for T₂S₂ it is ca. 1, which seems to be the first case where such intermediate mixing through parity violation is quantitatively predicted for spectroscopically accessible molecules. The consequences for the spectroscopic detection of molecular parity violation are discussed briefly also in relation to other molecules.     

The gas-phase elimination kinetics of 2-hydroxy-2-methylbutyric acid and 2-ethyl-2-hydroxybutyric acid

The elimination kinetics of the title compounds have been examined over the temperature range of 270–320°C and pressure range of 19–117 torr. The reactions, carried out in seasoned vessels, with the free-radical suppressor toluene always present, are homogeneous, unimolecular, and follow a first-order rate law. The products of 2-hydroxy-2-methylbutyric acid are 2-butanone, CO, and H₂O; while of 2-ethyl-2-hydroxybutyric acid are 3-pentanone, CO, and H₂O. The rate coefficient is expressed by the following Arrhenius equation: for 2-hydroxy-2-methylbutyric acid, log k₁(s^?1 = (12.87 ± 0.19) ? (171.2 ± 2.1) kJ mol^?1 (2.303 RT)^?1; and for 2-ethyl 2-hydroxybutyric acid, log k₁s^?1) = (12.13 ± 0.34) ? (159.4 ± 3.7) kJ mol^?1 (2.303 RT)^?1. Augmentation of alkyl bulkiness at the 2-position of the 2-hydroxycarboxylic acids showed an increase in the rate of dehydration. The electron release of alkyl groups, rather than steric acceleration, appears to enhance the pyrolysis decomposition of these substrates. These reactions are believed to proceed through a semi-polar five-membered cyclic transition type of mechanism. © 1995 John Wiley & Sons, Inc.