Enantiosymmetric polymerisation

Some cadmium compounds, including simple salts, were revealed to be excellent catalysts for the enantiosymmetric polymerisation of propylene sulphide [156,157], For instance, the proportion of isotactic diads in the polypropylene sulphide) sample obtained in polymerisation with the cadmium (7 )-tartrate catalyst was more than 95%, higher than the 69% which was characteristic of a polymer sample prepared using the zinc (i )-tartrate catalyst [158]. The superior stereoselectivity of the cadmium (i )-tartrate catalyst is also borne out by the more effective separation into fractions having opposite optical rotations of the polypropylene sulphide) yielded by cadmium tartrate, compared with that yielded by zinc (i )-tartrate. Note the quite different behaviour of these two catalysts in terms of their stereoelectivity in the polymerisation of propylene sulphide only very slight optical activity was found for the polypropylene sulphide) sample prepared using cadmium tartrate, whereas that associated with the polymer sample obtained with zinc tartrate was found to have a much higher value [158]. 

Characterise the stereoselective (enantiosymmetric) polymerisation and stereoselective (enantioasymmetric) polymerisation of heterocyclic monomers. Give examples. 

Polymerisations of tiiranes in the presence of coordination catalysts containing multinuclear species have been extensively studied in terms of their stereoselective and stereoelective behaviour. For monosubstituted tiiranes, the polymerisation can proceed enantiosymmetrically and lead to a mixture of isotactic chains of opposite configurations. By using optically active catalysts, the polymerisation may occur enantioasymmetrically, with the enchainment of only one of the two enantiomers. 

The above stereospecific tiirane polymerisations have generally been run in heterogeneous systems. Such conditions essentially make it impossible to determine the detailed structure of active species involved in these polymerisations. Thus, enantiosymmetric and enantioasymmetric polymerisations of propylene sulphide have also been studied in a homogeneous phase by using chiral cadmium thiolates of cysteine esters and chiral cadmium carboxylates of cysteine and methionine [157,160-164]. The most studied is living polymerisation using the cadmium derivative of the isopropyl ester of (.S)-cysteine [160] ... 

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