Ruthenium-Assisted Tellurium Abstraction in Bis(thiophen-2-yl) Ditelluride

The reaction of [RuCl₂(CO)₃]₂ and Te₂Tpn₂ (Tpn=thiophen-2-yl, C₄H₃S) in the absence of light resulted in the formation of cct-[RuCl₂(CO)₂(TeTpn₂)₂] ( 1 ) [cis(Cl)-cis(CO)-trans(TeTpn₂)] and TeTpn₂ ( 2 ) together with the precipitation of tellurium. The complex 1 and the monotelluride 2 were characterized by NMR spectroscopy and single-crystal X-ray diffraction. The decomposition of Te₂Tpn₂ to TeTpn₂ has been monitored by ¹²⁵Te NMR spectroscopy and seemed to be faster than the ligand substitution in [RuCl₂(CO)₃]₂ by TeTpn₂. A catalytic cycle is proposed for the decomposition of Te₂Tpn₂ to TeTpn₂ based on the PBE0-D3/def2-TZVP calculations.     

Fractionation of pulp and precipitated CaCO3–pulp composites: effects on sheet properties of selective CaCO3 precipitation onto fiber size fractions

Cellulose - CaCO3-pulp composite was prepared via precipitation of calcium hydroxide in the presence of pulp. In order to investigate the precipitation selectivity and mechanism, the substrate...     

Experimental and theoretical investigations of tellurium(IV) diimides and imidotelluroxanes: X-ray structures of B(C6F5)3 adducts of OTe(mu-NtBu)2TeNtBu, [OTe(mu-NtBu)2Te(mu-O)]2 and tBuNH2

The hydrolysis of (t)BuNTe(mu-N(t)Bu)(2)TeN(t)Bu (1) with 1 or 2 equiv of (C(6)F(5))(3)B.H(2)O results in the successive replacement of terminal imido groups by oxo ligands to give the telluroxane-Lewis acid adducts (C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)TeN(t)Bu (2) and [(C(6)F(5))(3)B.OTe(mu-N(t)Bu)(2)Te(mu-O)](2) (3), which were characterized by multinuclear NMR spectroscopy and X-ray crystallography. The Te=O distance in 2 is 1.870(2) A. The di-adduct 3 involves the association of four (t)()BuNTeO monomers to give a tetramer in which both terminal Te=O groups [d(TeO) = 1.866(3) A] are coordinated to B(C(6)F(5))(3). The central Te(2)O(2) ring in 3 is distinctly unsymmetrical [d(TeO) = 1.912(3) and 2.088(2) A]. The X-ray structure of (C(6)F(5))(3)B.NH(2)(t)()Bu (4), the byproduct of these hydrolysis reactions, is also reported. The geometries and energies of tellurium(IV) diimides and imido telluroxanes were determined using quantum chemical calculations. The calculated energies for the reactions E(NR)(2) + Te(NR)(2) (E = S, Se, Te; R = H, Me, (t)Bu, SiMe(3)) confirm that cyclodimerization of tellurium(IV) diimides is strongly exothermic. In the mixed-chalcogen systems, the cycloaddition is energetically favorable for the Se/Te combination. The calculated energies for the further oligomerization of the dimers XE(mu-NMe)(2)EX (E = Se, Te; X = NMe, O) indicate that the formation of tetramers is strongly exothermic for the tellurium systems but endothermic (X = NMe) or thermoneutral (X = O) for the selenium systems, consistent with experimental observations.     

Experimental and theoretical investigations of structural trends for selenium(IV) imides and oxides: X-ray structure of Se3(NAd)2

The thermal decomposition of Se(NAd)(2) (Ad = 1-adamantyl) in THF was monitored by (77)Se NMR and shown to give the novel cyclic selenium imide Se(3)(NAd)(2) as one of the products. An X-ray structural determination showed that Se(3)(NAd)(2) is a puckered five-membered ring with d(Se-Se) = 2.404(1) A and |d(Se-N)| = 1.873(4) A. On the basis of (77)Se NMR data, other decomposition products include the six-membered ring Se(3)(NAd)(3), and the four-membered rings AdNSe(micro-NAd)(2)SeO and OSe(micro-NAd)(2)SeO. The energies for the cyclodimerization of E(NR)(2) and RNEO (E = S, Se; R = H, Me, (t)Bu, SiMe(3)), and the cycloaddition reactions of RNSeO with E(NR)(2), RNSO(2) with Se(NR)(2), and S(NR)(2) with Se(NR)(2) have been calculated at MP2, CCSD, and CCSD(T) levels of theory using the cc-pVDZ basis sets and B3PW91/6-31G* optimized geometries. Sulfur(IV) and selenium(IV) diimide monomers are predicted to be stable, the sole exception being Se(NSiMe(3))(2) that shows a tendency toward cyclodimerization. The cyclodimerization energy for RNSeO and the cycloaddition reaction energies of RNSeO with Se(NR)(2) as well as that of RNSO(2) with Se(NR)(2) are negative, consistent with the observed formation of OSe(micro-N(t)Bu)(2)SeO, OSe(micro-N(t)Bu)(2)SeN(t)Bu, and O(2)S(micro-N(t)Bu)(2)SeN(t)Bu, respectively. Cycloaddition is unlikely when one of the reactants is a sulfur(IV) diimide.     

Structure and Bonding in Bis(1‐naphthyl) Diselenide and Bis{[2‐(N,N‐dimethylamino)methyl]phenyl} Tetraselenide,and Their Brominated Derivatives

The formation and crystal structures of bis(1‐naphthyl) diselenide ( 1 ) and bis{[2‐(N,N‐dimethylamino)methyl]phenyl} tetraselenide ( 2 ) are described. Whereas 1 can be produced in good yields, 2 is formed only as a minor product together with the known main product, bis{[2‐(N,N‐dimethylamino)methyl]phenyl} diselenide. The composition of the reaction mixture is semi‐quantitatively estimated by ⁷⁷Se NMR spectroscopy and DFT calculations. The effect of the n²→σ*(Se–Se) and π→σ*(Se–Se) secondary bonding interactions on the Se–Se bonds is discussed both by DFT calculations and comparison with literature, as available. The bromination of 1 yields monomeric (1‐naphthyl)selenenyl bromide ( 3 ) in good yields. That of the reaction mixture of (C₆H₄CH₂NMe₂)Se_x (x = 2–4) and Se₈ afforded (C₆H₄CH₂NMe₂H)₂[SeBr₄] ( 4 ) and (C₆H₄CH₂NMe₂H)₂[SeBr₆] ( 5 ) in addition to (C₆H₄CH₂NMe₂)SeBr, which has been previously reported.     

Trace metal analysis of coal fly ash collected plain and on a quartz fibre filter

A simple, uniform procedure has been developed for microwave-based digestion of fly ash samples collected from the hoppers of an electrostatic precipitator (ESP), or collected from flue gases on a heat-resistant quartz fibre filter and for subsequent atomic absorption spectrometric analysis of trace metals (Be, Cd, Co, Cr, Cu, Mn, Ni, Pb, V and Zn). HNO₃, HCl, HF and mixtures have been tested as digestion acids. The combination of HNO₃ and HF has been found to be efficient for the digestion of fly ash samples with and without quartz fibre filter material. In spite of the complicated matrix, results with satisfactory accuracy and precision (relative standard deviation below 10% for most of the elements) have been obtained. In the case of analysis of fly ash together with a quartz fibre filter, the calibration curve has to be determined by standard addition to a blank solution containing a dissolved blank quartz fibre filter.     

Molecular valence calculations on cyclohexasulfur,cycloheptasulfur, and cyclooctasulfur

A theoretical study of homocyclic sulfur species S₆, S₇, and S₈ was carried out using a molecular valence method involving stepwise approximations for orthogonality and core-valence interactions. The valence shell orbitals are described at the minimal basis level. The geometries of the molecules are predicted well as compared with other theoretical studies and the experimental values. The slight overestimation of the SS bond length is typical to the nonpolarized basis sets. The energies of the valence orbitals are well in accord with the conventional all-electron ab initio results. The trend in the stabilities of the three molecules is discussed. The present method provides an attractive possibility to study homocyclic and heterocyclic systems involving heavier chalcogens with no increase of the computing time.     

Self-diffusion of (31)Si and (71)Ge in relaxed Si(0.20)Ge(0.80) layers

Self-diffusion of implanted (31)Si and (71)Ge in relaxed Si(0.20)Ge(0.80) layers has been studied in the temperature range 730-950 degrees C by means of a modified radiotracer technique. The temperature dependences of the diffusion coefficients were found to be Arrhenius-type with activation enthalpies of 3.6 eV and 3.5 eV and preexponential factors of 7.5 x 10(-3) m(2) s(-1) and 8.1 x 10(-3) m(2) s(-1) for (31)Si and (71)Ge , respectively. These results suggest that, as in Ge, in Si(0.20)Ge(0.80) both (31)Si and (71)Ge diffuse via a vacancy mechanism. Since in Si(0.20)Ge(0.80) (71)Ge diffuses only slightly faster than (31)Si , in self-diffusion studies on Si-Ge (71)Ge radioisotopes may be used as substitutes for the "uncomfortably" short-lived (31)Si radiotracer atoms.     

Model-based optimization of ultrasonic transducers

Numerical simulation and automated optimization of Langevin-type ultrasonic transducers are investigated. These kind of transducers are standard components in various applications of high-power ultrasonics such as ultrasonic cleaning and chemical processing. Vibration of the transducer is simulated numerically by standard finite element method and the dimensions and shape parameters of a transducer are optimized with respect to different criteria. The novelty value of this work is the combination of the simulation model and the optimization problem by efficient automatic differentiation techniques. The capabilities of this approach are demonstrated with practical test cases in which various aspects of the operation of a transducer are improved.