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Cocatalyst influence in selective oligomerization: effect on activity, catalyst stability, and 1-Hexane/1-Octene selectivity in the ethylene trimerization and tetramerization reaction

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McGuinness, DS and Rucklidge, AJ and Tooze, RP and Slawin, AMZ (2007) Cocatalyst influence in selective oligomerization: effect on activity, catalyst stability, and 1-Hexane/1-Octene selectivity in the ethylene trimerization and tetramerization reaction. Organometallics, 26 (10). pp. 2561-2569. ISSN 0276-7333

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Abstract

The trimerization and tetramerization of ethylene to 1-hexene and 1-octene with a Cr/PNP/AlEt3 catalyst
system, in combination with a variety of cocatalysts, has been investigated. The cocatalysts B(C6F5)3 (1),
Al(OC6F5)3 (2), [(Et2O)2H][Al(OC6F5)4] (3), [Ph3C][Ta(OC6F5)6] (4), (Et2O)Al{OCH(C6F5)2}3 (5), (Et2O)-
Al{OC(CF3)3}3 (6), [Ph3C][Al{OC(CF3)3}4] (7), [Ph3C][AlF{OC(CF3)3}3] (8), [Ph3C][{(F3C)3CO}3Al-
F-Al{OC(CF3)3}3] (9), and [Ph3C][CB11H6Br6] (10) have been evaluated. The relative selectivity to
1-hexene and 1-octene obtained shows a strong dependence on the nature of the cocatalyst, and a range
of selectivities from <5% C8 (90% C6) to 72%C8 have been observed. The stability of several cocatalysts
toward AlEt3 has been studied, and the poor performance of 1 and 2 is linked to degradation of the
cocatalyst through ethyl group exchange with AlEt3. In contrast, the [Al{OC(CF3)3}4]- anion in 7 is
much more stable and gives rise to a highly active and longer lived catalyst. The overall productivity and
selectivity of the catalyst is dependent upon both cocatalyst stability and the nature of the anion present,
and a reason for this effect has been suggested. Selectivity control by the cocatalyst has been ascribed
to interaction of the anion with the active Cr center.

Item Type: Article
Journal or Publication Title: Organometallics
Publisher: American Chemical Society
Page Range: pp. 2561-2569
ISSN: 0276-7333
Identification Number - DOI: 10.1021/om070029c
Additional Information:

Copyright © 2007 American Chemical Society

Date Deposited: 07 Apr 2008 14:25
Last Modified: 18 Nov 2014 03:34
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