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2 Possible Back-Skip of Growing Chain. 3). The possible occurrence of a back-skip of the chain for catalytic systems based on C2 -symmetric metallocenes would not change the chirality of the transition state for the monomer insertion and hence would not influence the corresponding polymer stereostructure. 65 In fact, it is reasonable to expect an increase in the frequency of chain back-skip by reducing the monomer concentration and hence the frequency of monomer insertion. For the case of catalytic systems based on C1 -symmetric metallocenes, a driving force for the occurrence of the back-skip phenomenon related to the energy difference between the two diastereomeric situations obtained by exchanging the relative positions of monomer and chain can be added.

Electroneutrality conditions impose that metal atoms on this lateral cut are bonded to four Cl atoms bridge bonded to further metal atoms and one Cl atom not bridge bonded and that coordination position is left free. Two nonequivalent coordination positions, which will become available to monomer and growing polymer chain, inward and outward, are indicated by i and o, respectively (see text). 40 CHIRALITY OF CATALYSTS FOR STEREOSPECIFIC POLYMERIZATIONS to five Cl atoms only. Four of these are bridged to further metal atoms and are then more strongly bonded.

9). 9a, respectively. Dotted lines indicate rotation of coordinated monomer around θ0 whose activation energy is assumed to be lower than (or comparable to) activation energy for secondary insertion. Activation energies, which in this framework are relevant to regiospecificity, are also indicated. GAETANO GUERRA, LUIGI CAVALLO and PAOLO CORRADINI Insertion step Coordination step Coordination step Primary insertion 35 Insertion step Secondary insertion Monomer rotation d c b (a ) ∆E ‡pri a ∆E ‡sec Aspecific site e Monomer rotation Free energy c d b ∆E ‡pri,r (b ) a ∆E ‡sec,r Syndiospecific site d Monomer rotation c e ∆E ‡diss,w b ∆E ‡sec,w a (c ) Isospecific site Alkene free Alkene bound Pn+1 (olef.

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Advanced Organic Chemistry by Warren


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