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Probing the effects of ligand structure on activity and selectivity of Cr(III) complexes for ethylene oligomerisation and polymerisation

Moulin, J. O., Evans, J., McGuinness, D. S., Reid, G., Rucklidge, A. J., Tooze, R. P. & Tromp, M., 2008, In : Dalton Transactions. 2019, 9, p. 1177-1185 9 p.

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  • Probing the effects of ligand structure on activity and selectivity of Cr(iii) complexes

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DOI

  • Jerome O. Moulin
  • John Evans
  • David S. McGuinness
  • Gillian Reid
  • Adam J. Rucklidge
  • Robert P. Tooze
  • Moniek Tromp

A series of distorted octahedral Cr(III) complexes containing tridentate S-,S/O- or N-donor ligands comprised of three distinct architectures: facultative {S(CH(2)CH(2)SC(10)H(21))(2) (L(1)) and O(CH(2)CH(2)SC(10)H(21))(2)(L(2))}, tripodal {MeC(CH(2)S(n)C(4)H(9))(3) (L(3)), MeC(CH(2)SC(10)H(21))(3) (L(4))} and macrocyclic {(C(10)H(21))[9]aneN(3) (L(5)), (C(10)H(21))(3)[9] aneN(3) (L(6)), with [9] aneN(3) = 1,4,7- triazacyclononane} are reported and characterised spectroscopically. Activation of [CrCl(3)( L)] with MMAO produces very active ethylene trimerisation, oligomerisation and polymerisation catalysts, with significant dependence of the product distribution upon the ligand type present. The properties of the parent [CrCl(3)(L)] complexes are probed by cyclic voltammetry, UV-visible, EPR, EXAFS and XANES measurements, and the effects upon activation with Me(3)Al investigated similarly. Treatment with excess Me3Al leads to substitution of Cl ligands by Me groups, generation of an EPR silent Cr species (consistent with a change in the oxidation state of the Cr to either Cr(II) or Cr(IV)) and substantial dissociation of the neutral S and S/O-donor ligands.

Original languageEnglish
Pages (from-to)1177-1185
Number of pages9
JournalDalton Transactions
Volume2019
Issue number9
Publication statusPublished - 2008
Externally publishedYes

    Keywords

  • THIOETHER MACROCYCLIC CHEMISTRY, OLEFIN POLYMERIZATION, TRIAZACYCLOHEXANE COMPLEXES, CRYSTAL-STRUCTURE, OXIDATION-STATE, ALPHA-OLEFINS, CR-PNP, CATALYSTS, TRIMERIZATION, CHROMIUM

ID: 107575428