Divalent Samarium: Synthesis and Crystal Structures of Sm4OCl6 and KSm2Cl5

Single crystals of Sm₄OCl₆ and KSm₂Cl₅ have been obtained by metallothermic reductions of SmCl₃ with lithium (in the presence of Sm₂O₃ or SmOCl) and potassium, respectively, at elevated temperatures in sealed tantalum containers. Sm₄OCl₆ (hexagonal, P6₃mc, Z = 2, a = 946.59(4), c = 717.88(4) pm) and KSm₂Cl₅ (monoclinic, P2₁/c, Z = 4, a = 888.06(6), b = 784.81(5), c = 1262.77(8) pm, ß = 90.085(6)°) are true divalent samarium compounds, Sm₄OCl₆ with remarkably short Sm²⁺–O^2? distances (236.0, 237.6 (3x) pm) within the [Sm₄O] tetrahedron.     

Substituent control of hydrogen bonding in palladium(II)-pyrazole complexes

Inter- and intramolecular hydrogen bonding of an N-H group in pyrazole complexes was studied using ligands with two different groups at pyrazole C-3 and C-5. At C-5, groups such as methyl, i-propyl, phenyl, or tert-butyl were present. At C-3, side chains L-CH(2)- and L-CH(2)CH(2)- (L = thioether or phosphine) ensured formation of chelates to a cis-dichloropalladium(II) fragment through side-chain atom L and the pyrazole nitrogen closest to the side chain. The significance of the ligands is that by placing a ligating side chain on a ring carbon (C-3), rather than on a ring nitrogen, the ring nitrogen not bound to the metal and its attached proton are available for hydrogen bonding. As desired, seven chelate complexes examined by X-ray diffraction all showed intramolecular hydrogen bonding between the pyrazole N-H and a chloride ligand in the cis position. In addition, however, intermolecular hydrogen bonding could be controlled by the substituent at C-5: complexes with either a methyl at C-5 or no substituent there showed significant intermolecular hydrogen bonding interactions, which were completely avoided by placing a tert-butyl group at C-5. The acidity of two complexes in acetonitrile solutions was estimated to be closer to that of pyridinium ion than those of imidazolium or triethylammonium ions.     

Longitudinal nuclear relaxation measurements in hcp H2

Measurements of T₁ in the hep phase of H₂, over the temperature range 2°–12°K and the ortho concentration range between 0.5 and 0.97 are presented. At temperatures below 10°K, the thermally activated self-diffusion is negligible and the mechanism for nuclear relaxation is that attributed by Moryia and Motizuki and by Harris to intramolecular dipolar interaction, modulated by intennolecular electric quadrupole-quadrupole (EQQ) interaction. The gaussian approximation for the correlation function was used by these authors to predict T₁. From the comparison between experiment and theory, we determine the EQQ parameter Γ/k_B to be 0.67°K. Above 10°K the effect of diffusion influences T₁, and the experimental results for an 88 per cent ortho H₂ sample up to the melting point suggest that the relaxation mechanisms resulting from EQQ interaction and diffusion are not independent of one another.     

Determination of the atmospheric neutrino spectra with the Fréjus detector

The combined analysis of the final event set of data on neutrino interactions inside the detector, upward going stopping muons and horizontal muons recorded in the Fréjus experiment is presented. The absolute atmospheric neutrino spectra in the energy range for electron neutrinos and for muon neutrinos are determined. Based on the parameterization of Volkova for thev ^µ a spectral index of =2.66±0.05 is obtained from the ratio of horizontal muons over upward going stopping muons and from the measurement of the energy loss of horizontal muons inside the detector. The neutrino spectra are compared with various flux calculations. They do not show any evidence for neutrino oscillations in agreement with earlier analyses of the Fréjus data.Now atUniversity of Michigan, Ann Arbor, USA