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Carbon-bridged diphosphine ligands for chromium-catalysed ethylene tetramerisation and trimerisation reactions


Overett, MJ and Blann, K and Bollmann, A and de Villiers, R and Dixon, JT and Killian, E and Maumela, MC and Maumela, H and McGuinness, DS and Morgan, DH and Rucklidge, A and Slawin, AMZ, Carbon-bridged diphosphine ligands for chromium-catalysed ethylene tetramerisation and trimerisation reactions, Journal of Molecular Catalysis A: Chemical, 283, (1-2) pp. 114-119. ISSN 1381-1169 (2008) [Refereed Article]

DOI: doi:10.1016/j.molcata.2007.11.036


The use of carbon-bridged diphosphine ligands in chromium-catalysed ethylene tri- and tetramerisation reactions has been investigated. Two- and three-carbon spacer ligands all showed activity for selective oligomerisation, with a structure-selectivity correlation between P-Cr-P bite angle and 1-octene:1-hexene ratio evident. Activated chromium complexes of single carbon spacer diphosphines were also shown to be effective tetramerisation catalysts, provided that the ligand is innocent under the conditions of catalyst activation. A catalyst with the bis(diphenylphosphino)benzene ligand was found to be exceptionally active, although the combined 1-hexene and 1-octene selectivity was lower than with the best diphosphinoamine (PNP) ligands. The yield losses to by-products can to an extent be minimised by the use of high reaction temperatures and pressures. Unlike with the PNP-based systems, attempts to activate the Cr/bis(diphenylphosphino)benzene catalyst in situ from a chromium salt and free ligand resulted in low activity and high polymer formation. The effect of different phosphine substitution on catalyst selectivity was explored. Steric constraints around the catalytic centre (ortho-alkylphenyl phosphines) resulted in a shift towards 1-hexene formation, as with PNP catalysts. Additionally, the basicity of the phosphines appears to influence catalyst selectivity, with alkyl phosphines favouring trimerisation. An interplay between phosphine basicity and bridge structure is in evidence, however, as a catalyst containing a ligand with both basic phosphine atoms and a small bite angle was shown to be selective towards 1-octene. © 2007 Elsevier B.V. All rights reserved.

Item Details

Item Type:Refereed Article
Research Division:Chemical Sciences
Research Group:Inorganic chemistry
Research Field:Organometallic chemistry
Objective Division:Manufacturing
Objective Group:Industrial chemicals and related products
Objective Field:Organic industrial chemicals (excl. resins, rubber and plastics)
UTAS Author:McGuinness, DS (Dr David McGuinness)
ID Code:55262
Year Published:2008
Web of Science® Times Cited:71
Deposited By:Chemistry
Deposited On:2009-03-06
Last Modified:2009-05-01

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