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

Probing the effects of ligand structure on activity and selectivity of Cr(III) complexes for ethylene oligomerisation and polymerisation
Probing the effects of ligand structure on activity and selectivity of Cr(III) complexes for ethylene oligomerisation and polymerisation
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(CH2CH2SC10H21)2 (L2)}, tripodal {MeC(CH2SnC4H9)3 (L3), MeC(CH2SC10H21)3 (L4)} and macrocyclic {(C10H21)[9]aneN3 (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.
1477-9226
1177-1185
Moulin, Jerome O.
9beb2413-2de3-46dc-8a6e-5dc2fac0b29a
Evans, John
05890433-0155-49fe-a65d-38c90ea25c69
McGuinness, David S.
8b93fc01-6b9c-4d5b-b77b-6e992a783bde
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Rucklidge, Adam J.
1ebb74ef-c11b-43a0-9a34-689f36ff15a1
Tooze, Robert P.
9461ecde-9da0-42c6-a17f-6387bd8c5a7b
Tromp, Moniek
48c1ebbb-579c-42b6-83bb-7188c668b322
Moulin, Jerome O.
9beb2413-2de3-46dc-8a6e-5dc2fac0b29a
Evans, John
05890433-0155-49fe-a65d-38c90ea25c69
McGuinness, David S.
8b93fc01-6b9c-4d5b-b77b-6e992a783bde
Reid, Gillian
37d35b11-40ce-48c5-a68e-f6ce04cd4037
Rucklidge, Adam J.
1ebb74ef-c11b-43a0-9a34-689f36ff15a1
Tooze, Robert P.
9461ecde-9da0-42c6-a17f-6387bd8c5a7b
Tromp, Moniek
48c1ebbb-579c-42b6-83bb-7188c668b322

Moulin, Jerome O., Evans, John, McGuinness, David S., Reid, Gillian, Rucklidge, Adam J., Tooze, Robert P. and Tromp, Moniek (2008) Probing the effects of ligand structure on activity and selectivity of Cr(III) complexes for ethylene oligomerisation and polymerisation. Dalton Transactions, (9), 1177-1185. (doi:10.1039/b716078j). (PMID:18283378)

Record type: Article

Abstract

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(CH2CH2SC10H21)2 (L2)}, tripodal {MeC(CH2SnC4H9)3 (L3), MeC(CH2SC10H21)3 (L4)} and macrocyclic {(C10H21)[9]aneN3 (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.

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e-pub ahead of print date: 3 January 2008
Published date: 7 March 2008

Identifiers

Local EPrints ID: 146973
URI: http://eprints.soton.ac.uk/id/eprint/146973
ISSN: 1477-9226
PURE UUID: 135c67a7-e02f-4551-b1d5-42d8893ee75e
ORCID for Gillian Reid: ORCID iD orcid.org/0000-0001-5349-3468

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Date deposited: 23 Apr 2010 08:31
Last modified: 26 Nov 2019 02:03

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