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Reaction of Ni complexes with methylenecyclopropane: Binger, P.; Brinkmann, A.; McMeeking, J. Liebigs Ann. Chem. 1977, 1065. Recently, nickel complexes with a diimine ligand were found to bring about addition polymerization of cyclopentene. See ref 5b.
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note
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The results of the deuterium labeling study are more consistent with 1,2-insertion of the monomer than 2,1-insertion, but they do not exclude the mechanism of polymer growth via 2,1-insertion completely. Polymer growth mainly via 2,1-insertion and preferential hydrolysis of the polymer end via 1,2-insertion, which occurs much less frequently than 2,1-insertion, may also account for the results. Regioregularity of this polymerization, however, suggests that 1,2-insertion is more favorable than the above mechanism of polymer growth. The bulky monomer structure is suited for 1,2-insertion rather than 2,1-insertion.
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20
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0012291712
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note
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The structure of the end group was not determined by NMR spectroscopy. The latter chain transfer mechanism is less plausible because of severe ring strain of the polymer end formed via β-hydrogen elimination of the growing polymer end.
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