Polonium complex halides

Pseudohalides of Se in which the role of halogen is played by cyanide, thiocyanate or selenocyanate are known and, in the case of Se are much more stable with respect to disproportionation than are the halides themselves. Examples are Se(CN)2, Se2(CN)2, Se(SeCN)2, Se(SCN)2, Se2(SCN)2. The selenocyanate ion SeCN is ambidentate like the thiocyanate ion, etc., p. 325), being capable of ligating to metal centres via either N or Se, as in the osmium(IV) complexes [OsCl5(NCSe)], [OsCl5(SeCN)], and trans-[OsCU(NCSe)(SeCN)]2-.920) Tellurium and polonium pseudohalogen analogues include Te(CN)2 and Po(CN)4 but have been much... 

The basic salts of quadrivalent polonium, such as the sulfate and sele-nate, show a marked resemblance to those of tellurium and further resemblances appear in the quadrivalent halides, particularly in their complexing with halide ions in solution, while complexing of polonium(IV) with weak acids, such as acetic, oxalic and tartaric, seems to be more marked than is the case with tellurium. 

Table 6.8 gives stability constants for the complexes [FeX] and [HgX] for different halide ions while the stabilities of the Fe complexes decrease in the order F > CP > Br, those of the Hg complexes increase in the order F < CP < Br < P. More generally, in examinations of stability constants by Ahrland, Chatt and Davies, and by Schwarzenbach, the same sequence as for Fe + was observed for the lighter s- and /i-block cations, other early J-block metal cations, and lanthanoid and actinoid metal cations. These cations were collectively termed class (a) cations. The same sequence as for Hg complexes was observed for halide complexes of the later J-block metal ions, tellurium, polonium and thallium. These ions were collectively called class (b) cations. Similar patterns were found for other donor atoms ligands with O- and iV-donors form more stable complexes with class (a) cations, while those with S- and F-donors form more stable complexes with class (b) cations. 

Polonium Halides. Polonium halides are similar to those of tellurium, being volatile above 150° and soluble in organic solvents. They are readily hydrolyzed and form complexes, for example, Na2[PoX6], isomorphous with those of tellurium. There is tracer evidence for the existence of a volatile polonium fluoride. The metal is also soluble in hydrofluoric acid, and complex fluorides exist. 

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