The complex [q3-methylallyl)(~4-cycloocta-1,5-diene)nickel] hexafluorophosphate (2) was found to be an efficient catalyst for the oligomerization of styrene without using a Lewis acid. Oligomers and polymers with low degree of polymerization were obtained and characterized by GPC and NMR spectroscopy. Solvents and ligands have a strong effect on the catalyst activity, the molecular weight distributions and the polymer microstructure. The end groups were characterized in the case of the ligand-free and the tributylphosphine and tricyclohexylphosphinemodified systems. A terminal benzylidene group was observed except for the latter basic and bulky phosphine which led to a methylene terminal group. A mechanism involving a hydridonickel species is proposed.
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