Novel Cobalt Dichloride Complexes with Hindered Diphenylphosphine Ligands: Synthesis, Characterization, and Behavior in the Polymerization of Butadiene.

ABSTRACT: Two novel cobalt diphenylphosphine complexes were synthesized by reacting cobalt(II) chloride with tert-butyl(diphenyl)phosphine (P^tBuPh₂) and (S)-(+)neomenthyldiphenylphosphine [(S)-NMDPP]. The crystal structure of the former was determined by single-crystal X-ray diffraction studies. The two complexes were then used in combination with methylaluminoxane (MAO) for the polymerization of 1,3-butadiene: crystalline highly syndiotactic 1,2 poly(1,3-butadiene)s were obtained, with a 1,2 content and a syndiotactic index (percentage of syndiotactic triads [rr]) up to 95% and 85%, respectively. The results obtained further support and confirm what was already observed in the polymerization of 1,3-butadiene with CoCl₂(PRPh₂)₂-MAO (R = methyl, ethyl, normal-propyl, iso-propyl, and cyclohexyl): the nature of the phosphine ligand strongly affects the polymerization stereoselectivity, the polymer syndiotacticity increasing with increasing phosphine ligand steric hindrance.

SUBMITTER: Ricci G 

PROVIDER: S-EPMC6630202 | biostudies-literature | 2019 Jun

REPOSITORIES: biostudies-literature