Iron catalysts for the head-to-head dimerization of α-olefins and mechanistic implications for the production of linear α-olefins

Organometallics

Volumn 20, Issue 26, 2001, Pages 5738-5744

  Small, Brooke L ^a   Marcucci, A J ^a  

^a CHEVRON PHILLIPS CHEMICAL COMPANY LP   (United States)

Author keywords

[No Author keywords available]

Indexed keywords

IRON CATALYSTS; LINEAR OLEFINS; OLIGOMERIZATION; PYRIDINE BIS-IMINE IRON CATALYST; VINYLIDENE;

CATALYST ACTIVITY; CATALYSTS; COMPOSITION; COMPOSITION EFFECTS; DIMERIZATION; ETHYLENE; NUCLEAR MAGNETIC RESONANCE SPECTROSCOPY; PROPYLENE; REACTION KINETICS; STRUCTURE (COMPOSITION); SUBSTITUTION REACTIONS;

IRON COMPOUNDS;

EID: 0035945448     PISSN: 02767333     EISSN: None     Source Type: Journal    
DOI: 10.1021/om0105019     Document Type: Article

References (42)

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25. As note (35) in ref 9a of this paper reports, the exact nature of chain transfer (β-H elimination to metal vs β-H transfer to monomer) in the iron catalysts reported herein is not known. If hydride abstraction by incoming monomer is the actual mechanism, this process would likely occur with opposite regiochemistry from propagation, to form linear dimers. If abstraction occurs with the same regiochemistry (2,1) as propagation, then the resultant Fe-alkyl complex would produce only branched dimers, or in the analogous propylene polymerization systems, no n-butyl groups would be observed at the saturated chain ends. This said, it is worth nothing that several theoretical papers on both the Fe and the Co catalysts support a mechanism of β-H transfer rather than β-H elimination. See, for example: (a) Deng, L.; Margl, P.; Ziegler, T. J. Am. Chem. Soc. 1999, 121, 6479.
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30. (a) Small, B. L.; Brookhart, M. Polym. Prepr., Am. Chem. Soc. Div. Polym. Chem. 1998, 39, 213.
31. (b) Britovsek, G. J. P.; Gibson, V. C.; Kimberley, B. S.; Maddox, P. J.; McTavish, S. J.; Solan, G. A.; White, A. J. P.; Williams, D. J. Chem. Commun. 1998, 849.
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37. Small, B. L. University of North Carolina Doctoral Dissertation, Diss. Abstr. Int., B, 1999, 59 (12), UMI order number DA9914912.
38. Researchers at DuPont and BP have reported several examples of low comonomer incorporation using supported versions of these catalysts: (a) Bennett, A. M. A.; Feldman, J.; McCord, E. (DuPont) WO9962967, 1999.
39. (b) Kimberley, B. S.; Maddox, P. J.; Partington, S. R. (BP) WO9946302, 1999.
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41. Neutral trialkylaluminium compounds are used in the commercial ethylene oligomerization processes of Chevron Phillips (CPC) and BP. The GC analysis described in the text was performed on CPC commercial samples.
42. The calculate an accurate turnover number (TON), the formula weight of the precatalyst in needed. A closer look at some of the analytical data (CHN analysis) for some of the less sterically bulky complexes, such as those reported in ref 10d, seemed to indicate the presence of an equivalent of THF in the isolated solids. CHN analysis indicated that an equivalent of THF is present in complexes 1-5, and it is here noted that a formula weight of 540.3 was determined for 1 and subseuquently used in the TON calculation. Complex 1 was also analyzed by ICP, which gave the expected 10.3% iron content, indicating the presence of THF.