Abstract
14N chemical shifts and linewidths were determined for NO3− and NH3 in liquid ammonia solutions of thallium nitrate at concentrations between 0.07 and 10 M. The concentration dependences of the14NO3− shift and linewidth are consistent with the presence of C2v ion pairs at a 2:1 mole ratio of NH3 to TINO3 and C3v ion pairs at mole ratios of 3:1 or higher. Previous studies had indicated the formation of ion pairs at low concentrations. The small value of the14NO3− linewidth below 1 M suggests that these are contact ion pairs. Studies of the14NH3 linewidth as a function of thallium salt concentration indicate slow solvent exchange at very high concentrations.14NH3 exhibits a downfield shift upon incorporation into the solvation sphere of the Tl+NO3− ion pair, in constrast to upfield shifts reported for complexation with transition metal cations.
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