Structure-parameter and force-field refinement for lead dihalide molecules

Conclusions It has been shown for PbF₂ that one can process electron-diffraction data for molecules containing heavy atoms on the basis of atomic scattering amplitudes calculated with a relativistic approximation for the atomic electron density. The errors in calculating the atomicscattering amplitudes explain the previous discrepancies in the observed values for the Pb-Cl amplitudes in PbCl₂ derived in two independent researches. The differences between those values are now not so considerable, and they may be explained as due to experimental error or to the processing of the measurements in Hungary for most of the scattering angles having been performed without the relativistic corrections to the electron density.Our mean-square vibration amplitudes and the measured frequencies can be used with our semiempirical relationships for the force constants to determine the potential-energy parameters for those molecules and to estimate the vibrational frequencies for PbI₂, which have not been measured.I am indebted to Professor V. P. Spiridonov and staff at the vapor electron-diffraction laboratory at Moscow University for providing the observed values for the reduced molecular component of the scattering intensities for lead dihalides and for valuable comments in discussion on the draft.High-Temperature Institute, Academy of Sciences of the USSR. Translated from Zhurnal Strukturnoi Khimii, Vol. 32, No. 1, pp. 54–59, January–February, 1991.     

The structure of the 1-1-difluoroethylene radical anion and the factors determining the hyperfine interaction with 19F

A structure with a pyramidal -CF₂ group is shown to desribe satisfactorily hyperfine interactions in CH₂CF_$\text{2}$ radical anions within the framework of the INDO method. The factors responsible for the substantial difference in the degree of spin density delocalization on F in CH₂CF_$\text{2}$ and C₂F_$\text{4}$ are analyzed.     

Molybdenum-95 NMR spectra of some molybdenum carbony and related compounds

Molybdenum-95 NMR spectra have been measured for a selection of molybdenum carbonyl compounds and Mo(Σ-C₅H₅)(η-C₅H₅)(NO)(S₂CNMe₂). A chemical shift range of more than 1500 ppm is found. The chemical shifts and linewidths are discussed.     

Synthesis and spatial structure of the geometrical isomers of 4-substituted 1-tert-butyl-3-methyl-piperidin-4-ols and 4-acyloxy-1-tert-butyl-3-methylpiperidines

In order to study the interrelationship between the structure, reactivity, and spectroscopic characteristics of the stereoisomeric piperidines, starting from 1-tert-butyl-3-methylpiperidin-4-one the synthesis has been performed of the geometric isomers of some 4-substituted 1-tert-butyl-3-methylpiperidin-4-ols and 4-acyloxy-1-tert-butyl-3-methylpiperidines. The spatial structures of the compounds obtained have been determined by IR and PMR spectroscopy.Translated from Khimiya Geterotsiklicheskikh Soedinenii, No. 8, pp. 1056–1061, August, 1973.     

Automated determination of fluoride ion in the parts per milliard range

Fluoride, down to 2 ppM, has been determined by automated direct potentiometry using a fluoride ion-selective electrode. The method reduces the dilution and contamination effects of TISAB and takes the electrode response-time into consideration. The relative standard deviation for water samples is 1.5-1.8% and the recovery varies from 96 to 107%.     

Conformations of fused cycloalkanes in organometallic complexes : IV. The crystal and molecular structure of tricyclo-[6.4.0.02.7]dodeca-3,5-dienetricarbonyliron

The precise molecular structure of the title compound has been determined by single crystal X-ray diffractometry. It consists of a cyclohexadiene ring fused at the 5 and 6 positions to a cyclobutane ring which is in turn fused to a cyclohexane ring. The two six-membered rings are trans to each other with respect to the shared four-membered ring. The Fe(CO)₃ moiety is bound in the usual way to the conjugated diene portion of the cyclohexadiene ring. The feature of greatest interest is the mutual influence of the conformations of the two fused cycloalkane rings, whose intrinsically preferred conformations are mutually incompatible. Under the influence of the fused cyclohexadiene ring the C₄ ring would tend to be planar, while the cyclohexane ring would tend, of itself, to have a chair conformation. The actual result is a compromise, with the C₄ ring being folded by 15° along its diagonal and the C₆ ring having a conformation intermediate between planarity and a chair. Crystallographic data: space group, P2₁, Z = 2. Unit cell dimensions at 3°C are a = 6.176(1), b = 11.307(2), c = 9.781(2) Å and β = 92.89(2)°. A set of 1733 reflections having 2θ(Mo-K_α) < 63.7° and I > σ(I) was refined to convergence (R₁ = 0.055; R₂ = 0.034) with hydrogen atoms refined isotropically and all others anisotropically.     

Simulation of intermolecular and intramolecular interactions of nucleic acid subunits by means of atom–atom potential functions

Atom–atom potential functions for calculation of nonbonded interaction energies of nucleic acids are proposed. Quantitative reliability of the obtained results is checked by using the calculations of intermolecular interaction energy in crystals. Based on the calculations of the interaction energy of the nucleic acid bases the molecular mechanisms of spontaneous mutations are suggested.     

Connection between the electronic structure of tin in its compounds and the isomer shifts in the Mössbauer spectra

A formula is obtained which relates the isomer shifts in the Mössbauer spectra to the electronic structure of tin in its compounds. It is shown that these formulas describe the isomer shifts of various kinds of chemical compounds: tetravalent tin with -bonding (tin tetrahalides), tetravalent tin with no -bonding (compounds in which the tin is bound to alkyl, aryl, or metal carbonyl radicals), divalent tin, etc. The formulas are used to analyze the electronic structures of tin in compounds of these classes. It is shown that in tetravalent tin compounds with -bonding the isomer shift in the negative direction (with respect to -Sn) is due to the decreased number of 5s-valence electrons, and in the absence of -bonding, by an increase in the number of 5s-valence electrons.     

Synthesis and Properties of First Bis(fluoreno)crownophanes

Alkylation of 2,7-dihydroxy-9H-fluoren-9-one with 2-(2-chloroethoxy)ethanol, 2-[2-(2-chloroethoxy)-ethoxy]ethanol, and 2-{2-[2-(2-chloroethoxy)ethoxy]ethoxy}ethanol in dimethylformamide in the presence of potassium carbonate gave 78–80% of the corresponding diols which were treated with p-toluenesulfonyl chloride in a dioxanechloroform mixture in the presence of triethylamine at 0– 5°C (30 h). The resulting bis(p-toluene-sulfonates) were brought into condensation with 2,7-dihydroxy-9H-fluoren-9-one in a very dilute solution in dimethylformamide containing anhydrous potassium carbonate at 80–85°C. Appropriate treatment of the reaction mixture, followed by chromatographic purification afforded 53–27% of the first representatives of a new class of cyclophanes, bis(oxofluoreno)crownophanes. Raising the temperature to 95–105°C resulted in an appreciable decrease of the product yield. The yield of the target products did not increase on replacement of potassium carbonate by cesium carbonate.__________Translated from Zhurnal Organicheskoi Khimii, Vol. 41, No. 1, 2005, pp. 144–149.Original Russian Text Copyright © 2005 by Lyapunov, Kirichenko, Kulygina, Luk’yanenko.     

Synthesis of Sybstituted Isoxazoles and Pyrazoles Based on 1-Aryl-3,4,4-trichloro-3-buten-1-ones

3-Aryl-5-methylenehydroxyiminoisoxazoles were synthesized by reaction of 1-aryl-3,4,4-trichloro-3-buten-1-ones with hydroxylamine. Reactions of ketones with hydrazine provided pyrazole structures; therewith two pyrazole molecules underwent coupling affording 3-arylpyrazole-5-carbaldehyde azines.