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

journal contribution
posted on 2023-05-16, 23:19 authored by Moulin, JO, Evans, J, McGuinness, DS, Reid, G, Rucklidge, AJ, Tooze, RP, Tromp, M
A series of distorted octahedral Cr(iii) complexes containing tridentate S-, S/O- or N-donor ligands comprised of three distinct architectures: facultative {S(CH2CH2SC10H21) 2 (L1) and O(CH2CH2SC 10H21)2 (L2)}, tripodal {MeC(CH 2SnC4H9)3 (L 3), MeC(CH2SC10H21)3 (L4)} and macrocyclic {(C10H21)[9]aneN 3 (L5), (C10H21)3[9] aneN3 (L6), with [9]aneN3 = 1,4,7-triazacyclononane} are reported and characterised spectroscopically. Activation of [CrCl3(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 [CrCl3(L)] complexes are probed by cyclic voltammetry, UV-visible, EPR, EXAFS and XANES measurements, and the effects upon activation with Me3Al 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. © The Royal Society of Chemistry.

History

Publication title

Dalton Transactions

Volume

2008

Issue

9

Pagination

1177-1185

ISSN

1477-9226

Department/School

School of Natural Sciences

Publisher

The Royal Society of Chemistry

Place of publication

Cambridge

Repository Status

  • Restricted

Socio-economic Objectives

Organic industrial chemicals (excl. resins, rubber and plastics)

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