Oxygen donor complexes tetrachlorides

On the other hand, Dyrssen and Liem (1960) report (table 7) greater variation in both distribution ratios [for americium and europium extraction by dibutyl phosphoric acid (HDBP)] and in separation factors as a function of diluent. The separation factors and distribution coefficients are correlated (more or less consistently) inversely with the distribution ratio of the extractant between the phases. In this system, the largest separation factors are observed in n-hexane, chloroform, and carbon tetrachloride. Diluents capable of direct coordination (i.e., those possessing potential oxygen-donor atoms) are correlated with reduced distribution ratios and separation factors. The observations of greater separation factors in non-complexing diluents suggest that more effective separation is observed when the inner-coordination sphere of the hydrophobic complex is not disturbed. 

The relative basicity of carbonyl oxygen atoms can be measured by studying strength of hydrogen bonding between the carbonyl compound and a hydrogen donor such as phenol. In carbon tetrachloride, values of for 1 1 complex formation for the compounds shown have been measured. Rationalize the observed order of basicity. 

Even fewer complexes with nitrogen donor ligands have been reported and all are methyl cyanide adducts (Tables X and XI). Protactinium pentabromide forms a soluble 1 3 complex in contrast to the 1 1 complexes formed by niobium and tantalum pentahalides (46). Other actinide pentahalide-methyl cyanide complexes are still unknown. Protactinium tetrachloride, tetrabromide, and tetraiodide react with anhydrous, oxygen-free methyl cyanide to form slightly soluble 1 4 complexes (44, 48) which are isostructural with their actinide tetrahalide analogs. 

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