Cathode-catalyzed transesterification of alkylphosphonates

The cathodic electrolysis of aliphatic alcohols and alkylphosphonates in acetonitrile with 0.5 N Et₄NClO₄ as the base electrolyte leads to mono- and ditransesterified phosphonates. The yield and ratio of these products is a function of the nature of the starting reagents and amount of current passed.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 1, pp. 200–204, January, 1991.     

Investigations on surface diffusion in sparingly soluble monolayers at the gas/liquid interface using radiotracer technique

Summary A method is proposed for calculating surface selfdiffusion coefficients in sparingly soluble monolayers at fluid interfaces based on radiotracer measurements and allowing for counter geometry. On this basis an analysis of experimental results is possible without having to allow for processes competing with surface self-diffusion. Monolayers of various long-chainn-alcohols andn-alkane-carboxylic acids were studied in the area range between 0.23 nm²/molecule and 2.0 nm²/molecule. Surface self-diffusion coefficientsD _s were determinded only up to areas of 0.75 nm2/molecule since, in case of greater areas, the analysis of surface concentration becomes inexact due to the increasing influence of density convection. For the systems studied,D _s values lie in the order of 10^–5 cm²/s. In all compounds studied, the values ofD _s increase with area per molecule. In addition, dependence on the type of hydrophilic group and alkyl-chain length of monolayer molecules was proved. The results are discussed by means of various model concepts.

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Zusammenfassung Ein Verfahren zur Berechnung der Oberflächenselbstdiffusionskoeffizienten in schwerlöslichere Monoschichten an fluiden Phasengrenzen auf der Grundlage von Radiotracermessungen und unter Berücksichtigung der Zählrohrgeometrie wird vorgeschlagen. Auf dieser Basis ist eine Auswertung der Experimentalergebnisse möglich, ohne daß zur Oberflächenselbstdiffusion in Konkurrenz stehende Transportvorgänge berücksichtigt werden müssen. Untersucht wurden Monoschichten verschiedener längerkettigern-Alkanole undn-Alkancarbonsäuren im Flächenbereich zwischen 0,23 nm²/Molekül und 2 nm²/Molekül. OberflächenselbstdiffusionskoeffizientenD _s wurden nur bis zu Flächenwerten von 0,75 nm²/Molekül bestimmt, weil bei höheren Flächen die Auswertung der Oberflächenkonzentrationsänderungen wegen des zunehmenden Einflusses von Dichtekonvektion ungenau wird. DieD _s -Werte liegen für die untersuchten Systeme in der Größenordnung 10^–5 cm2/s. Bei allen untersuchten Verbindungen nehmen die Werte von D_s mit steigender Fläche pro Molekül zu. Außerdem wurde die Abhängigkeit von der Art der hydrophilen Gruppe und der Alkylkettenlänge der Monoschichtmoleküle nachgewiesen. Die Ergebnisse wurden anhand verschiedener Modellvorstellungen diskutiert.

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With 8 figures and 1 table     

Chalcogenide Exchange Reaction of [RGa(μ3-Te)]4 with Elemental Sulfur and Selenium: A Density Functional Theory Study

Thermodynamic and mechanistic features of the chalcogen exchange reaction between [RGa( ₃-Te)]₄ and elemental sulfur or selenium have been studied employing density functional theory (DFT) calculations using the BL3YP basis set and Stuttgart pseudopotentials. For [MeGa( ₃-E)]₄ (E=S, Se, Te) the correlation between the calculated parameters and diffraction data for their isolable analogs is greater than 98%. Each step of the conversion of [MeGa( ₃-Te)]₄ to [MeGa( ₃-E)]₄ via [Me₄Ga₄( ₃-Te)_4–x ( ₃-E) _x ] (E=S, Se) is predicted to occur as a series of isolated reactions. The entropy change for each chalcogen exchange is small in magnitude and corresponds to the degree of cage distortion within the cubane molecules. Calculations performed on [MeGa( ₃-Te)]₄...S₈ and [MeGa( ₃-Te)]₄-S suggest that an increase in electrophilicity of the gallium next to a surface bound tellurium may result in nucleophilic cage opening for which intermediate structures are calculated.     

Gold(III) complexes with imidazole,benzoxazole, purine and pyrimidine derivatives

Summary The synthesis and characterization of Au^III complexes with several heterocyclic ligands are reported. The compounds have general formula [AuX₃(L)], where L =N-methylimidazole (N-MeIz),N-ethylimidazole (N-EtIz),N-propylimidazole (N-PrIz), benzoxazole (BO), 2-methylbenzoxazole (2-MeBO), 2,5-dimethylbenzoxazole (2,5-diMeBO), 2-amino-pyrimidine (2-APm), 4(6) -hydroxy-pyrimidine [4(6)-hydrPm] or hypoxanthine (Hypox) and X = Cl or Br. Elemental analysis, conductivity measurements and spectral studies were used for the characterization of the complexes. A square-planar geometry withN-bonded heterocyclic ligands is suggested.     

An algebraic method that includes Gibbs minimization for performing phase equilibrium calculations for any number of components or phases

The most widely used technique for performing phase equilibria calculations is the K-value method (equality of chemical potentials). This paper proposes a more efficient algorithm to achieve the results that includes Gibbs minimization when we know the number of phases. Using the orthogonal derivatives, the tangent plane equation and mass balances, it is possible to reduce the Gibbs minimization procedure to the task of finding the solution of a system of non-linear equations. Such an operation is easier and faster than finding tangents or areas, and appears to converge as fast as the K-value method. Examples illustrate application of the new technique to two and three phases in equilibrium for binary and ternary mixtures.     

Single wall carbon nanotubes density of states: comparison of experiment and theory

We study the electronic structure of a variety of single wall carbon nanotubes and report density of states obtained with the Perdew–Burke–Ernzerhof (PBE) generalized gradient approximation and hybrid PBE0 approximation of density functional theory using Gaussian orbitals and periodic boundary conditions. PBE gives very good results for metallic tubes but the addition of a portion of exact exchange in the hybrid PBE0 functional worsens the agreement between experiment and theory. On the other hand, the PBE0 hybrid significantly improves the theoretical predictions (compared to PBE) for semiconducting tubes.     

The particle structure ofv-dimensional Ising models at low temperatures

In this work we study thev-dimensional Ising model at low temperatures and establish the existence of an upper gap in the energy-momentum spectrum of the two-point function forv3. Forv=2, it is known that this gap is absent.Supported in part by Conselho Nacional de Pesquisas (CNPq-Brazil), Universidade Federal de Minas Gerais (Brazil) and the National Science Foundation under Grant PHY76-17191     

Molecular structure of ethynylbenzene from electron diffraction and ab initio molecular orbital calculations

The molecular structure and benzene ring distortions of ethynylbenzene have been investigated by gas-phase electron diffraction and ab initio MO calculations at the HF/6-31G^* and 6-3G^** levels. Least-squares refinement of a model withC _2v, symmetry, with constraints from the MO calculations, yielded the following important bond distances and angles:r _g(C _i -C _o )=1.407±0.003 Å,r _g(C _o -C _m )=1.397±0.003 Å,r _g(C _m -C _p )=1.400±0.003 Å,r _g(Cr _i -CCH)=1.436 ±0.004 Å,r _g(C=C)=1.205±0.005 Å, C _o -C _i -C _o =119.8±0.4°. The deformation of the benzene ring of ethynylbenzene given by the MO calculations, including o-C_i-C_o=119.4°, is insensitive to the basis set used and agrees with that obtained by low-temperature X-ray crystallography for the phenylethynyl fragment, C₆H₅-CC-, in two different crystal environments. The partial substitution structure of ethynylbenzene from microwave spectroscopy is shown to be inaccurate in the ipso region of the benzene ring.     

Forbidden matrix proton spin flip satellites in trapped electron EPR spectra

Observation of the 35 GHz EPR spectrum of γ-irradiated 10 M NaOH/H₂O and 10 M NaOD/D₂O glassy ices at 77°K has revealed proton spin flip satellites associated with the trapped elctron EPR line. This suggests that forbidden satellite transitions contribute to the lineshape of the trapped electron line in the 9 GHz spectrum which has commonly been studied.     

A computational study of bond dissociation enthalpies in haloethenes

Carbon–hydrogen bond dissociation enthalpies (BDEs) were computed for all haloethenes, C₂H_4−nX_n (n=0–3, X=F, Cl, Br, I), at the B3LYP/6-311+G(3df,2p) level using isodesmic reactions. It was found that C–H bond strengths in the monohaloethenes varied substantially, by as much as 18 kJ mol⁻¹, dependent upon the bond's stereochemical position relative to the halogen. BDEs in the dihaloethanes varied in the order CX₂CH–H>(E)-CHXCX–H>(Z)-CHXCX–H. Trends in the computed bond enthalpies were discussed and explained on the basis of relative steric repulsions and hyperconjugative delocalization interactions, as determined from Natural Bond Orbital analysis.