Nickel Amino-Bis(phenol) Complexes for Copolymerization of Cyclohexene Oxide and Phthalic Anhydride

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Abstract
A series of air-stable nickel(II) complexes with various tetradentate diamino-bis(phenol)/(phenolate) ligands and coligands were synthesized. Six of these Ni[O2NN′] complexes were structurally characterized by single-crystal X-ray diffraction. The Ni[O2NN′] complexes were screened as catalysts for ring-opening copolymerization (ROCOP) of cyclohexene oxide (CHO) and phthalic anhydride (PA), utilizing bis(triphenylphosphine)iminium chloride (PPNCl) as a cocatalyst. It was determined that the catalytic activity for the Ni[O2NN′] complexes depended primarily on the coordinating coligands/counterions and the presence of a cocatalyst. Ni[O2NN′] complexes with acetate or chloride coligands selectively formed high molar mass polyesters with narrow dispersities (e.g. Mn = 14.5 kg mol–1 and Đ = Mw/Mn = 1.17), but only in the presence of the PPNCl cocatalyst. Ni[O2NN′] complexes with perchlorate counterions formed polymers containing a mixture of ester and ether linkages in the presence of PPNCl cocatalyst, and instead selectively formed polyether when no cocatalyst was used.
Funding Information
  • Department of Industry, Energy and Technology (NA)
  • Natural Sciences and Engineering Research Council of Canada (NA)
  • Canada Foundation for Innovation (NA)
  • Mitacs (NA)
  • Memorial University of Newfoundland (NA)
  • Graduate Program in Physics at UNIFAL-MG (NA)

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