The Effect of Solvent Variation on Nucleophilic Substitution Rates of Methyl Tosylate

Rates of the reactions between bromide ion and methyl tosylate have been determined in 12 solvents and extrapolated to infinite dilution. The data are correlated with Parker's solvent activity coefficients by means of an empirical equation of the type: logk^s – logk⁰ = A log⁰γ + B with the constants A = 0.788 and B = 0,108 and a correlation coefficient of 0.983.     

Gehinderte ligandenbewegungen in übergangsmetallkomplexen : V. 1H-NMR-untersuchung der bewegungen des olefinliganden in cyclopentadienyl-mangan-dicarbonyl-tetramethoxyäthylen

The methoxy signals in the ¹H NMR spectrum of cyclopentadienylmanganese dicarbonyl tetramethoxyethylene, C₅H₅Mn(CO)₂[C₂(OCH₃)₄], show a definite temperature-dependence. In CS₂ solution the variations of the signals are observed within a single temperature range, while in toluene-d₈ two regions of change are found to exist. These data are explained on the basis of two mutually independent ligand movements: a hindered rotation of the olefin ligand around the metalligand bond (ΔG³₁₉₄ = 9.8 ± 0.6 kcal/mol), and a hindered movement of the four methoxy groups (ΔG³₂₆₃ = 13.8 ± 0.3 kcal/mol, both in toluene-d₈. Chiral conformations of the ligand are assumed to be formed when the movement of the methoxy substituents ceases.     

Messung der spezifischen Wärme von abschreckend kondensierten Indium-, Blei- und Wismut-Schichten bei tiefer Temperatur

Thin metal films are evaporated onto a cooled Be-foil at 25–32 °K in high vacuum. After condensation the films have a large degree of disorder. The specific heat is measured in the temperature range from 5–8 °K after condensation and after annealing. No differences in the specific heat are found for disordered and annealed In- and Pb-films. The specific heat of amorphous Bi-films, however, is 1.7 times larger than that of crystalline films. The results are discussed together with investigations of disordered films by superconducting tunneling.