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The MWD and 14C distribution of poly(2-alkylbutadienes) obtained in the presence of bis-[( -crotyl-14C)nickel iodide] in benzene solution has been studied. It is shown that both the polymer chain length and the nature of the 2-alkyl substituent in polydiene play a decisive role in determining the dissociation degree of dimeric -allylic active sites. The correlation between MWD and the ratio of the monomeric species of active sites to the dimeric ones is established.