L. Beaufort et al. / Journal of Molecular Catalysis A: Chemical 283 (2008) 77–82
81
Table 2
Influence of the co-catalyst on the oligomerization activity of complex 3 at various temperatures
Co-catalyst
Oligomerization activity (g C2H4 mmol−1 h−1
)
30 ◦C
35 ◦C
40 ◦C
45 ◦C
MMAO
DEAC
EADC
150
123
153
121
110
116
78
79
103
97
110
113
Reaction conditions: 0.5 mmol of (MeC(CH2NPCp3)3)NiBr2 (3) in the presence of an aluminum co-catalyst (Al/Ni = 800), 10 bar of C2H4 (constant pressure), 5 mL
of n-heptane for 1 h.
Table 3
Oligomer distributions obtained with various transition-metal complexes at 30 ◦C
Complex
Oligomer distribution (mol%)a
C4
C6
>C6
(PhC(CH2NPPh3)3)NiBr2 (2)
(PhC(CH2NPPh3)3)FeCl2 (5)
(PhC(CH2NPPh3)3)PdCl2 (6)
(PhC(CH2NPPh3)3)Cu(OTf)2 (7)
49
50
4
33
26
93
50
18
23
3
30
20
Reaction conditions: 0.5 mmol of catalyst in the presence of MMAO (Al/M = 800), 10 bar of C2H4 (constant pressure), 5 mL of n-heptane for 1 h.
a
Determined by GC analysis.
Although the four metal complexes examined in this study
reacted with ethylene at about the same rate, they afforded
mixtures of oligomers (mainly butenes and hexenes) with signif-
icantly different selectivities (Table 3). Nickel and iron catalytic
species (2 and 5, respectively) favored butene formation (up
to 50 mol% of the product distribution) together with a lesser
amount of higher oligomers (mostly hexenes), whereas palla-
dium and copper complexes 6 and 7 produced more hexenes
than butenes. Palladium complex 6, in particular, displayed
an impressive selectivity, affording almost exclusively hexenes
from ethylene.
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This work was generously supported by a BP-Solvay grant
to L.B.