Benzene chelated lithium salts

Evidence is presented which shows that a chelated cation is a distinct, long-lived chemical species and that different chelated cations may coexist in solution as discrete observable species. Investigation of the anion-cation interaction shows that chelated salts in benzene exist as tight ion pairs down to the limit of spectrometer sensitivity. The effect of chelating agent on ion pair separation is considered. Finally we describe a series of experiments conducted in mixed solvents, the results of which reveal a stereospecific association of aromatic solvent molecules with a chelated lithium salt. 

The unusual properties of polytertiaryamine chelated lithium salts have been noted (6). The high solubility and conductivity of chelated lithium halides in benzene raise a number of important and interesting questions concerning the role of the aromatic solvent since these chelated... 

Table XI. Solubilities of Chelated Lithium Salts in Benzene...

The data in Table V were obtained by sequential treatment of the initial sample with sodium iodide and lithium chloride. Complexation with sodium iodide was done in a heptane-benzene slurry. The sparingly soluble sodium iodide chelate was isolated by filtering the mixture. The remaining solution was concentrated, and the residue obtained was contacted with lithium chloride in pentane. After stirring this heterogeneous mixture, a solid lithium chloride chelate complex was isolated by filtration. Decomposition of the alkali-metal salt complexes followed by recovery and analysis of the polyamine components showed that the sodium iodide complex contained 82.6% n-HMTP while the LiCl complex contained 94.8% N,N -c-PMPP. Table V shows that the initial polyamine sample contained 48.8 and 11.4% of these ligands, respectively. 

---