Synthesis of mixed-ligand cobalt complexes and their applications in high cis-1,4-selective butadiene polymerization

Wen Liu, Weijing Pan, Peng Wang, Wei Li, Jingshan Mu, Gengsheng Weng, Xiaoyu Jia, Dirong Gong, Kuo-Wei Huang

Research output: Contribution to journalArticlepeer-review

14 Scopus citations

Abstract

Incomplete oxidation of (N-di-tert-butylphosphino)-6-(2-methyl-2’H-benzoimidazole)-2-aminepyridine dichlorocobalt (PN3CoCl2) in DMF results in a unique co-crystal I formed with three parts including DMF, unit A and unit B complex with Co1 and Co2, respectively, (PN3 ligand in unit A: (N-di-tert-butylphosphino)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine, and O=PN3 ligand in unit B: (N-di-tert-butylphosphinoxide)-6-(2’-methyl-2’H-benzoimidazole)-2-aminepyridine) with 1:1:1 molar ratio. Co1 and Co2 complexes both display a five-coordinated distorted-square-pyramidal geometry around the metal center. The Co1 center is coordinated with PN3 ligand via two N atoms from pyridine, benzoimidazole moiety as well as one P atom, and the Co2 center is coordinated with the oxidized ligandO=PN3 via two N atoms from pyridine, benzoimidazole moiety as well as one O atom from DMF molecule, while the oxidized phosphine moiety (O=P) being excluded from the coordination sphere. Activated with AlEt2Cl, the co-crystallized complexes I are able to actively convert butadiene to polybutadiene, affording cis-1,4 polybutadiene with cis-1,4 unit up to 95.5-97.8% and number average molecular weight of cal. 105g/mol. The high cis-1,4 selectivity and monomodal GPC curve of resultant polymer imply that the identical active species generated from two distinctive cobalt centers.
Original languageEnglish (US)
Pages (from-to)132-138
Number of pages7
JournalInorganica Chimica Acta
Volume436
DOIs
StatePublished - Aug 5 2015

ASJC Scopus subject areas

  • Materials Chemistry
  • Physical and Theoretical Chemistry
  • Inorganic Chemistry

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