dc.description |
A value of Ï 0.58 ± 0.05 has been obtained for the deuterium fractionation factor of the hydrogen-bonded complex AcO<sup>â </sup>â ¯(HOAc)n from <sup>1</sup>H n.m.r. studies of solutions of potassium acetate in AcOH and 97% AcODâ 3% AcOH. The result is used to account for the kinetic solvent isotope effect k AcO<sup>â </sup> <sup>AcOH</sup>/k AcO<sup>â </sup> <sup>AcOD</sup> 0.66 ± 0.10 measured for formation of acetic anhydride from 2,4,6-trinitrophenyl acetate in AcOH and AcOD in the presence of potassium acetate. The equilibrium solvent isotope effect on complex formation between 2,4,6-trinitrophenol and acetate ion in AcOH and 97% AcOD-3% AcOH, K <sup>AcOH</sup>/K <sup>AcOD</sup> 0.83 ± 0.1, leads to a value Ï ca. 0.7 for the complex [2,4,6-(NO2)3C6H2O â ¯ H â ¯ OAc]<sup>â </sup>. |