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Novel Cobalt Dichloride Complexes with Hindered Diphenylphosphine Ligands: Synthesis, Characterization, and Behavior
Giovanni Ricci1, Giuseppe Leone2, Ivana Pierro3
1CNR-Istituto per lo Studio delle Macromolecole (ISMAC), via A. Corti 12, 20133 Milano, Italy. giovanni.ricci@ismac.cnr.it.
Abstract:
Two novel cobalt diphenylphosphine complexes were synthesized by reacting cobalt(II) chloride with tert-butyl(diphenyl)phosphine (PBuPh2) 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.
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