Study of the reactivity of chalcogen hexafluorides with graphite

The intercalation reaction of chalcogen hexafluorides, EF₆ (E=S, Se, Te), with graphite was investigated. It occured only under a fluorine atmosphere and first stage intercalation compounds were obtained with TeF₆ or SeF₆, as well as a partial graphite fluorination. SF₆ did not intercalate but catalyzed the complete fluorination of graphite. All compounds were characterized by X-ray diffraction, thermogravimetric analysis, infrared and ¹⁹F NMR spectroscopies. Entities, such as TeF₆ and SeF₆ were identified. Others, such as EF₇⁻, EF₈²⁻, …, and possible SeF_n polymeric forms could exist. In all cases, the presence of fluorinated graphite was found.     

Induction effects on IR-predissociation spectra of (SF6)2, (SiF4)2 and (SiH4)2

The observed difference in transition strength for (SF₆)₂, (SiF₄)₂ and (SiH₄)₂ IR-predissociation spectra is explained by induction effects (μ₀₁²/R₁₂⁶) which have to be included in the interaction Hamiltonian in addition to the dominant dipole-dipole term (μ₀₁²/R₁₂³).     

Formation of SF5 in electron attachment to SF6; swarm and beam results reconciled

Based on the results of recent swarm experiments, it has been proposed that the increase in the cross section for SF₅⁻ formation observed at an electron energy, E_e of about 0.3 eV in electron beam studies of electron attachment to SF₆ is due to the combined (opposing) effects of the vibrational heating of the molecule by the attached electron, which enhances the dissociation of the nascent (SF₆⁻)^* ion, and the reduction of the cross section for capture (s-wave) of the electron by SF₆ with increasing E_e. Further, it has been shown that the dissociation reaction is endothermic by 0.12 eV, and that, contrary to previous suggestions, there is no potential barrier to this dissociation reaction. Now we have carried out electron beam studies of the SF₆ attachment reaction in Berlin at gas temperatures, T_g, over the range 300 to 920 K and in Innsbruck at T_g below 300 K. These studies have provided support for the above proposals concerning the appearance of the SF₅⁻ peak and for a reaction endothermicity of 0.12 eV. Thus these studies have clarified the doubts about the products of the SF₆ attachment reaction at low electron energy.     

Rhenium(I) methoxo carbonyl complexes containing tetraphosphine or triphosphine ligands; facile separation and X-ray crystallographic studies of d/l- and meso-[{Re2(μ-OMe)2(CO)6}2(μ,μ′-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetra-phosphadecane)]

Reaction of the activated mixture of Re₂(CO)_10, Me₃NO and MeOH with a 1:1 mixture of rac (d/l)- and meso-1,1,4,7,10,10-hexaphenyl-1,4,7,10-tetraphosphadecane (hptpd) yields a mixture of (d/l)- and meso-[{Re₂(μ-OMe)₂(CO)₆}₂(μ,μ′-hptpd)] 1. The diastereomers can be easily separated by selective dissolution of d/l-1 in benzene, and give clearly distinguishable ¹H- and ³¹P-NMR spectra. The fluxional behavior of d/l-1 in solution has been studied by variable-temperature ¹H- and ³¹P-{¹H}-NMR spectroscopy. The crystal structures of both d/l- and meso-1 have been determined. Both molecules consist of two {Re₂(μ-OMe)₂(CO)₆} moieties which are bridged by the two P---CH₂---CH₂---P moieties of the hptpd ligand. Whilst the molecules of meso-1 possess crystallographic i-symmetry, those of d/l-1 do not have any crystallographic symmetry. These diastereomers therefore give clearly distinguishable Raman spectra in the solid state. Reaction of tris[2-(diphenylphosphino)ethyl]phosphine (tdppep) with the activated mixture affords the complex [{Re₂(μ-OMe)₂(CO)₆}(μ,η²-tdppep)] 2, and the analogous reaction involving bis[2-diphenylphospinoethyl)phenylphosphine (triphos) gives [{Re₂(μ-OMe)₂(CO)₆}(μ,μ′,η³-triphos){Re₂(CO)₉}] 3 and [{Re₂(μ-OMe)₂(CO)₆}(μ,η²-triphos)] 4.     

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.     

Photoabsorption spectra of H2S, CH3SH and SO2 near the sulfur K edge

Photoabsorption spectra of the isolated sulfur containing molecules H₂S, CH₃SH and SO₂ are measured at high resolution near the sulfur K edge, using synchrotron radiation. Resonances are observed in the discrete and continuum parts of the spectra. The most intense resonances are shown to result from virtual orbital effects on the basis of comparisons with the L edge photoabsorption spectra (H₂S, SO₂), the equivalent core model (SO₂) and low-energy electron scattering measurements (H₂S, SO₂).     

Infrared and Raman spectra and phase transition of the SF6 crystal. Anharmonic interactions and two-phonon infrared absorption

The infrared and Raman spectra of the two crystalline forms of SF₆ have been investigated at 97 and 9 K, respectively. The experimental data on the high-temperature form are fully consistent with the known crystal structure while inferences on the unknown structure of the other form have been made and an orthorombic D_2h structure isomorphous with that of other hexafluorides is proposed. In the infrared-active fundamental region large LO-TO splittings due to long-range electrostatic interactions have been observed. The combination regions of the infrared spectrum show broad two-phonon absorption bands in both forms. The energy and density of two-phonon states have been obtained on the basis of an intermolecular harmonic dipole-dipole interaction. The intensity and line profile of two-phonon bands has been studied with the help of a recently developed Green function treatment. A renormalized two-phonon density of states has been calculated. It is shown that the indirect intramolecular mechanism through third-order terms in the intramolecular potential gives the main contribution to two-phonon band intensity. A good agreement with experiments is obtained.     

Oxygen potential and phase equilibria in the Te-Sb2O3-Sb2O4 pseudoternary part of the Sb-Te-O system at elevated temperatures

Employing the electrochemical cells with the solid oxide electrolyte

Kanthal + Re, Te(l), TeO₂(s)O⁻² air, Pt

Pt + Re, Sb₂O₃(s), Sb₂O₄(s)O⁻² air, Pt

Pt + Re, Sb₂O₃(s), Sb₂O₄(s), Te(l)O⁻² air, Pt

the equilibrium oxygen potential in the pseudobinary Te-TeO₂, Sb₂O₃-Sb₂O₄ and in the Sb₂O₃-Sb₂O₄-Te pseudoternary systems was determined in the temperature range 700-1173 K. In addition, the pseudobinary sections Sb₂O₃-Te, Sb₂O₃-Sb₂O₄ (1:1)-Te and Sb₂O₄-Te were examined by DTA in the temperature range 500-1300 K. Using these results the evolution of the pseudoternary system with temperature can be suggested. It was found that, at 718 K, a ternary eutectic with a composition close to pure Te appears in the system. At a higher temperature, 920 K, another liquid phase is formed, which is characteristic of the ternary four-phase equilibrium L₂ + Sb₂O₄(s) + Sb₂O₃(s) = L₁.     

Use of central-field potentials for describing H2(D2) elastic scattering by other molecules

Differential elastic scattering cross sections have been measured for the systems H₂ + O₂, SF₆, NH₃, CO and CH₄ and for D₂ + O₂, SF₆, and NH₃ using crossed molecular beams. These experiments represent a wide variation in the size, anisotropy and initial relative collision energy E of the scattering partners, and of the corresponding de Broglie wavelengths. In all cases, rapid quantum oscillations have been resolved. From these differential cross sections, central-field potentials have been obtained which were independent of the energy and the isotopic composition of the hydrogen molecule used, as required for such potentials to be physically meaningful. Therefore, anisotropy effects do not seem important in describing the differential elastic scattering of these H₂(D₂) systems.     

Luminescence properties of CdTe QDs embedded in Zn5(CO3)2(OH)6 matrix

CdTe@Zn₅(CO₃)₂(OH)₆ composites were synthesized by a hydrothermal method. CdTe@Zn₅(CO₃)₂(OH)₆ composite nanospheres were characterized via X-ray diffraction, scanning electron microscopy, energydispersive X-ray spectroscopy, and photoluminescence (PL). The hydrothermal reaction time and the mole ratios of Zn/Te played important roles in the growth and fluorescence intensity of CdTe@Zn₅(CO₃)₂(OH)₆ composites. The composite powders showed peak PL at 578 nm at 1.6 times the intensity of powdered CdTe QDs. CdTe@Zn₅(CO₃)₂(OH)₆ exhibited a strong yellow fluorescence emission, and its preparation method was easy and economical. Therefore, CdTe@Zn₅(CO₃)₂(OH)₆ offers potential applications in biological markers and light-emitting diodes.     

AB initio study of the regular polyhedral molecules N4, P4, As4, N8, P8 and As8

Ab initio pseudopotential SCF calculations were performed on tetrahedral X₄ molecules using double-zeta basis sets with and without d functions. The inclusion of d orbitals shortens the bond lengths, stabilizes the X₄ structures and intensifies the electron density inside the tetrahedron. The cubic X₈ molecules, calculated without d AOs, are not predicted to be more stable than 2X₄. Repulsions between parallel bonds in X₈ may compensate the lack of ring strain.     

A localized molecular orbital study on the bonding of> Mo3S4]2Mo> and> Mo3S4]CuI> versus (C6H6)2Cr and C6H6Cr(CO)3

The energy-localized CNDO/2 molecular orbitais have been calculated for the clusters containing molybdenum, > {Mo₃S₄₂Mo}⁸⁺ and> Mo₃S₄]CuI> ⁴⁺, versus the prototype arene-metal sandwich (C₆H₆)₂Cr and half-sandwich complexes C₆H₆Cr(CO)₃. The bonding characteristics of these compounds are described from a localization bonding viewpoint. There are two typical M-arene and M-[Mo₃S₄] bondings. One is formed by electron donation from the three-center two-electron π-bonds in the arene or [Mo₃S₄]⁴⁺ ligands into the vacant hybrid orbitais of the “stranger” metal atom. In the other M-arene or M-[Mo₃S₄] bond there is very little donation by the lone electron pair occupying the d AOs of the “stranger” metal atom to the arene or [Mo₃S₄]⁴⁺ ligands. The analogy of the ligand [Mo₃S₄]⁴⁺ in the clusters studied with the ligand benzene is also briefly discussed.     

NMR spectra of salicylohydroxamic acid in DMSO-d6 solution: a DFT study

The ¹H, ¹³C and ¹H, ¹³C COSY NMR spectra of salicylohydroxamic acid (sha) were measured in DMSO-d₆ solution. The B3LYP GIAO method with the 6-311++G(d,p) basis set was chosen to reproduce the experimental spectra. All possible zusammen and entgegen conformers of monomeric sha were computed. After geometry optimisation (B3LYP/6-311++G(d,p)) only nine independent models of the molecule were shown to be stable. Additionally, the NMR chemical shifts of the Onsager model of the most stable monomer were calculated. The computed chemical shifts for the labile protons for all aforementioned geometries meaningfully underestimated experimental results suggesting the existence of the H-bonded structure of sha in DMSO solution. The most probable two dimeric structures along with two solvent-bounded aggregates were subsequently calculated at the same level of theory. The best agreement was obtained for sha H-bonded with two DMSO molecules (confirmed by the absence of concentration effect). The relative error not exceeding 10 and 4% for chemical shifts in ¹H and ¹³C NMR spectra of sha–(DMSO)₂, respectively, showed that the applied method with the B3LYP/6-311++G(d,p) basis set was efficient to predict the NMR shifts of a compound with strong H-bonds. Thus, this allows to assign properly NMR resonances to specific structure formed in DMSO solution.     

The temperature dependence of the two positronium bubble states in liquid SF6

Positron lifetime measurements have been performed on liquid SF₆ in the temperature range from −45°C to 71°C (T_c = 45.65°C). The positron lifetime spectra were resolved into four lifetime components. In the order of increasing lifetimes the four lifetime components are associated with the decay of para-positronium (p-Ps), free positrons, ortho-positronium (o-Ps) from a small bubble state, and o-Ps from a large bubble state. The lifetime of o-Ps annihilating from the large bubble state τ₄ increases from 5.7 ns at −45°C to 19.5 ns at 53°C. The lifetime of o-Ps annihilating from the small bubble state τ₃ was found to be 2–2.5 ns in the main part of the temperature range studied. Apparently, this is the first observation of two different o-Ps states in a liquid. The intensity I₄ (I₃) increases (decreases) from 16.9% (16%) at −45°C to 47.2% (6.4%) at the critical point while above I₃ and I₄ are essentially temperature independent. The large Ps bubble state seems to be similar to the Ps bubble state found in most liquids.     

Observation Of Mode Selective Vibrational Excitation Of SF6 By Collisions With 4–10 eV Li And H Ions

Structured time of flight spectra of both Li⁺ and H⁺ ions scattered from ground state SF₆, have been measured at angles (5.0° v_c.m. 16.6°) less than the rainbow angle at E_c.m., = 4.3 eV and 9.7 eV, respectively. The structure can be arttributed to vibrational excitation of the v₃ mode by H⁺ and excitation of the v₄ mode by Li⁺. The relative transition probabilities obey a Poisson distribution and can be explained by a simple forced oscillator model.     

Novel iodoammonium cations: Synthesis and characterization of o-C6H4(NH2)2IX (X = I, AsF6, AlI4)

The new iodoammonium salts o-C₆H₄(NH₂)₂I⁺I⁻ (1) and o-C₆H₄(NH₂)₂I⁺ AsF₆⁻ (2) were prepared by reaction of o-phenylene diamine with I₂ or I₃⁺AsF₆⁻, respectively. Compound 1 reacts with AlI₃ yielding quantitatively the corresponding tetraiodoaluminate o-C₆H₄(NH₂)₂I⁺AlI₄⁻ (3). The species were characterized by chemical analysis, vibrational (IR and Raman) and temperature-dependent ¹H NMR spectropscopy. Direct evidence for a N---I bond was found in the Raman spectra of 1, 2 and 3 (ν(NI) = 599–600 cm⁻¹).     

Polarized infrared and Raman spectra of CsHSeO4 and CsDSeO4 single crystals

The polarized absorption infrared spectra of CsHSeO₄ and CsDSeO₄ single crystals and polarized Raman spectra of the CsHSeO₄ single crystal were measured at room temperature. The polarization features of the internal vibrations of the HSeO⁻₄ ions are predicted on the basis of the X-ray structure assuming strong couping between the vibrations of the two shortest Se---O bonds and an intermediate Se---O bond. The bending methods γOH and δOH of a hydrogen bond appear at 805 cm⁻ and 1258 cm⁻¹, respectively. The νOH absorption has the ABC structure due to Fermi resonance of νOH with the overtones of the δOH and γOH vibrations. A similar shape of the νOH band is observed in the Raman spectra. The νOD absorption has a different shape from that of νOH. Intra-chain coupling was observed for the νOH and νOD vibrations.     

Structural and theoretical studies of Xe(OChF5)2 and [XeOChF5][AsF6] (Ch = Se, Te)

The XeOSeF₅⁺ cation has been synthesized for the first time and characterized in solution by ¹⁹F, ⁷⁷Se and ¹²⁹Xe NMR spectroscopy and in the solid state by X-ray crystallography and Raman spectroscopy with AsF₆⁻ as its counter anion. The X-ray crystal structures of the tellurium analogue and of the Xe(OChF₅)₂ derivatives have also been determined: [XeOChF₅][AsF₆] crystallize in tetragonal systems, P4/n, a=6.1356(1) Å, c=13.8232(2) Å, V=520.383(14) Å³, Z=2 and R₁=0.0453 at −60°C (Te) and a=6.1195(7) Å, c=13.0315(2) Å, V=488.01(8) Å³, Z=2 and R₁=0.0730 at −113°C (Se); Xe(OTeF₅)₂ crystallizes in a monoclinic system, P2₁/c, a=10.289(2) Å, b=9.605(2) Å, c=10.478(2) Å, β=106.599(4)°, V=992.3(3) Å³, Z=4 and R₁=0.0680 at −127°C; Xe(OSeF₅)₂ crystallizes in a triclinic system, , a=8.3859(6) Å, c=12.0355(13) Å, V=732.98(11) Å³, Z=3 and R₁=0.0504 at −45°C. The energy minimized geometries and vibrational frequencies of the XeOChF₅⁺ cations and Xe(OChF₅)₂ were calculated using density functional theory, allowing for definitive assignments of their experimental vibrational spectra.     

Gas-phase stability of cluster ions SF m + (SF6) n with m = 0–5 and n = 1–3

The gas-phase stabilities of cluster ions SF⁺_m (SF₆)_n with m = 0−5 were determined by using a high pressure mass spectrometer. The bond energies of SF⁺_m (SF₆)₁ were found to be less than 10 kcal/mol and to decrease with m = 0 → 5. There appear to be rather large gaps in the bond energies between n = 1 and 2 for the clusters SF⁺_m (SF₆)_n with m = 0−4. The structures of SF⁺₅, SF⁺ (SF₆)₁, SF⁺₃ (SF₆)₁, and SF⁺₅ (SF₆)₁ were investigated by ab initio molecular orbital calculations. For SF⁺₅, the D_3h geometry is found to be most stable andC_4v is a transition state of the Berry pseudorotation. For the ion-molecule complexes, the “on-top hat” models were found to be the most stable structures.     

Reaction of [(C6H6)RuCl2]2 with 7,8-benzoquinoline and 8-hydroxyquinoline

The reaction of [(C₆H₆)RuCl₂]₂ with 7,8-benzoquinoline and 8-hydroxyquinoline in methanol were performed. The obtained complexes have been studied by IR, UV–VIS, ¹H and ¹³C NMR spectroscopy and X-ray crystallography. In the reaction with 8-hydroxyquinoline the arene ruthenium(II) complex oxidized to Ru(III). The electronic spectra of the obtained compounds have been calculated using the TDDFT method. Magnetic properties of [Ru(C₉H₆NO)₃] · CH₃OH complex suggest the antiferromagnetic coupling of the ruthenium centers in the crystal lattice. EPR spectrum of [Ru(C₉H₆NO)₃] · CH₃OH compound indicates single isotropic line only characteristic for Ru³⁺ with spin equal to 1/2.