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The oxidation state of the transition metal (Mt) active centre is the most disputable question in the polymerization of olefins by Ziegler-Natta (ZN) and metallocene complexes. In this paper the importance and the changes of the Mt ac- tive centres are presented and discussed on the basis of a charge percolation mecha- nism (CPM) of olefin polymerization. Mt atoms can exist in different oxidation states and can be easily transformed from one to another state during activation. In all cases, the Mt atoms are present in several oxidation states, i.e. ,M t+(n-1) ,M t+(n) to Mt+(n+1), producing an irregular charge distribution over the support surface. There is a tendency to equalize the oxidation states by a charge transfer from Mt+(n-1) (do- nor) to Mt+(n+1) (acceptor). This cannot occur since the different oxidation states are highly separated on the support. However, monomer molecules are adsorbed on the support producing clusters with stacked -bonds, making a -bond bridge between a donor and an acceptor. Once a bridge is formed (percolation moment), charge trans- fer occurs. The donor and acceptor equalize their oxidation states simultaneously with the polymerization of the monomer. The polymer chain is desorbed from the support, freeing the surface for subsequent monomer adsorption. The whole process is repeated with the oxidation-reduction of other donor-acceptor ensembles.

The charge percolation mechanism and simulation of Ziegler-Natta polymerizations. Part III. Oxidation states of transition metals