Isomerization of olefins in a two-phase system by homogeneous water-soluble nickel complexes

Article abstract of DOI:10.1016/S0022-328X(97)00615-3

The first example of nickel catalyzed isomerization of olefins in a two-phase system is reported. Provided that the water-soluble ligand is properly tailored and that the Broensted acid is suitably selected, the catalytic system appears relatively stable and high catalytic activity can be reached.

Full text of DOI:10.1016/S0022-328X(97)00615-3

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Journal of Organometallic Chemistry 553 1998 469–471
Isomerization of olefins in a two-phase system by homogeneous
water-soluble nickel complexes
a
b
a,)
Herve Bricout , Andre Mortreux , Eric Monflier
´
´
a
UniÕersite d’Artois, Faculte des Sciences Jean Perrin, Laboratoire de Physico-Chimie des Interfaces et Applications, Rue Jean SouÕraz, Sac
´
´
postal 18-62307 Lens, France
b
Laboratoire de Catalyse Heterogene et Homogene, URA CNRS 402, ENSCL, Batiment C7, B.P. 108-59652 VilleneuÕe d’Ascq Cedex, France
´ ´
`
`
ˆ
Received 27 August 1997; received in revised form 19 September 1997
Abstract
The first example of nickel catalyzed isomerization of olefins in a two-phase system is reported. Provided that the water-soluble ligand
is properly tailored and that the Bronsted acid is suitably selected, the catalytic system appears relatively stable and high catalytic activity
¨
can be reached. q 1998 Elsevier Science S.A.
Keywords: Isomerization; Nickel; Water soluble phosphines; Two-phase system
1. Introduction
2. Materials and methods
Liquidrliquid two-phase catalysis is one of the most
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In a typical experiment, Ni COD 35 mg , DPPBTS
2
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important current topics of catalysis 1,2 . Indeed, by
using a wide range of water-soluble transition metal,
this approach has been applied successfully to numerous
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212 mg-synthesized according to Ref. 23 and water
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5 g or a mixture of water 5 g and methanol 5 g ,
were introduced under nitrogen into a glass tube reactor.
After stirring with magnetic bar for 2 h at 808C, the
solution exhibited a orange color and the insoluble
Ni COD has disappeared. This solution was then
transferred into a mixture of allylbenzene 750 mg ,
toluene 6.5 g and hydrochloric acid 407 mg of a 1.25
N aqueous solution . The medium was stirred at 1000
rpm at 808C and the reaction was monitored by quanti-
tative gas chromatographic analysis of aliquot samples
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reactions such as hydroformylation 3,4 , hydrogenation
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5,6 , carbonylation 7–9 , oligomerization 10 , car-
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bon–carbon coupling 11–13 , isomerization 14–17
and its industrial feasibility has been demonstrated by
Hœchst in the case of the hydroformylation of propene
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2
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into butyraldehyde 3,4 . Although one patent claimed
the nickel catalyzed addition of hydrogen cyanide to
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carbon–carbon double bonds 18 and that some water-
soluble zerovalent complexes of nickel have been syn-
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of the organic layer CP Sil 5-CB, 25 m=0.32 mm .
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thesized 19–22 , the use of this transition metal in
biphasic catalysis has so far been ignored.
In this context, we report herein the first example of
alkenes isomerization by water-soluble nickel com-
plexes in a two-phase system. The catalytic system
3. Results and discussion
Typical results with allylbenzene as model substrate
are reported in Table 1. We first investigated the activi-
ties obtained with the sodium salt of trisulfonated triph-
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consists of bis cycloocta-1,5-diene nickel 0 , a water-
soluble phosphine and a Bronsted acid dissolved in
¨
water or in a waterrmethanol mixture in order to
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enylphosphine TPPTS as phosphine. The results ob-
tained in water or in hydroalcoholic medium with this
common water-soluble phosphine are rather disappoint-
increase the mass transfer between aqueous and organic
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layers Scheme 1 .
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ing entries 1 to 3 . Indeed, isomerization occurred only
)
in the presence of Bronsted acids and a total loss of
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Corresponding author. Fax: q33-3-21-79-17-17; E-mail: mon-
catalytic activity was observed after 5–10 min reaction.
flier@univ-artois.fr.
0022-328Xr98r$19.00 q 1998 Elsevier Science S.A. All rights reserved.

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H. Bricout et al.rJournal of Organometallic Chemistry 553 1998 469–471
Scheme 1.
For instance, with trifluoroacetic acid, the allylbenzene
conversion reached rapidly 7% but stopped after 15 min
entries 2 and 3 . This result and the fast color change
between aqueous and organic layers. Consequently, the
behaviour of the nickelrDPPBTSracid system has been
investigated mainly in a biphasic hydroalcoholic
medium.
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of the aqueous layer red-orange to bright green indi-
cate clearly a catalytic species decay under these experi-
mental conditions.
We studied the role of the counteranion on the
reaction rate and on the trans to cis b-methylstyrene
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The above results and the well-know stability of
nickelrdiphosphine complexes in homogeneous medium
ratio entries 8 to 12 . Best results in terms of initial
activity have been obtained with acids possessing coor-
dinating anions such hydrogen chloride or hydrogen
iodide. Furthermore, in contrast with reactions con-
ducted with non-coordinating anions, the catalytic sys-
tem appeared more stable with these acids; indicating
that the coordinating-anions have a stabilizing effect on
the catalytic species. From a stereoselectivity point of
view, coordinating anions led to lower trans to cis
b-methylstyrene ratio. As a matter of fact, the transrcis
ratio reached 1.2 and 5.0 with HPF6 and HI and,
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24–26 led us to examine the behavior of a chelating
water-soluble phosphine like the sodium salt of tetrasul-
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fonated 1,4-bis diphenylphosphino butane DPPBTS .
Interestingly, the catalytic activity was preserved with
this ligand and allylbenzene conversion in methanol free
medium reached 92% after 48 h entry 6 . It should be
noticed that no reaction was observed in the absence of
nickel precursor or acid entries 4 and 5 . As expected
for weakly water-soluble substrates like allylbenzene,
entries 7 and 8 show that the reaction rate is greatly
improved by adding methanol to the medium and sug-
gest that the rate determining step is the mass transfer
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respectively entries 9 and 11 . It must be pointed out
that this trans to cis methylstyrene ratio increases in
the course of the reaction whatever the experimental
Table 1
Nickel catalyzed isomerization of allylbenzene in two-phase systema
y1
c
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Entry
Catalytic System
Phosphane
Polar layer
Initial TOF h
Allylbenzene conversion Transrcis ratioe
Acidb
1 h
48 hd
1 h
48 h
1
2
3
TPPTS
TPPTS
TPPTS
DPPBTS
y
DPPBTS
DPPBTS
DPPBTS
DPPBTS
DPPBTS
DPPBTS
DPPBTS
y
y
H2O
H2O
H2OrCH3OH
H2O
H2O
H2O
0
8
7
0
0
0
7
6
0
0
10
47
67
52
34
45
77
0
0
7
6
0
0
92
98
98
66
45
98
99
0
y
y
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CF3CO2 H 4
11.5
11.4
y
11.5
11.4
y
Ž .
CF3CO2 H 4
4
y
5g
6
CF3CO2 H 4
y
y
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CF3CO2 H 4
CF3CO2 H 4
CF3CO2 H 4
HPF6
HBF4
HI 4
HCl 4
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HCl 4
6
5.6
6.1
5.0
5.0
4.7
1.2
4.1
y
5.6
6.2
5.4
5.1
4.8
1.9
5.3
y
H2OrCH3OHf
H2OrCH3OH
H2OrCH3OH
H2OrCH3OH
H2OrCH3OH
H2OrCH3OH
H2OrCH3OH
33
71
63
52
84
106
0
Ž .
7
8
9
10
11
12
13g
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Ž .
4
Ž .
4
Ž .
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a
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Reaction conditions: Ni COD 2: 0.13 mmol; phosphine: 0.52 mmol eq. P; allylbenzene: 6.5 mmol; toluene: 6.5 g; Polar layer without cosolvent:
water: 5 g; polar phase with cosolvent: water: 5 g; methanol: 5 g; T: 808C; bthe acid to nickel ratio is given in brackets. c Mol of initially
converted allylbenzene per mol of nickel per hour. d Unoptimized reaction time. eTrans to cis-b-methylstyrene ratio. f Water: 5 g; methanol: 1.7 g.
g This control experiment carried out without nickel and DPPBTS proves undoubtedly that the isomerization is not catalyzed by the Bronsted acid.
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H. Bricout et al.rJournal of Organometallic Chemistry 553 1998 469–471
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conditions; indicating that the initial production of the
isomers is kinetically controlled. Finally, it is worth
mentioning that no addition product with water, hydro-
chloric or hydroiodic acid has been observed in the
experiments.
especially in cyclodimerisation and oligomerization re-
actions, can be expected with these complexes in bipha-
sic catalysis.
The nickelrdiphosphinerHCl catalytic system is also
efficient for the isomerization of other olefins. For
instance, hex-1-ene isomerization into hex-2-ene and
hex-3-ene can be achieved with an initial turnover
frequency of 500 hy1. At hex-1-ene complete conver-
sion, the hex-3-ene to hex-2-ene ratio reached 2.5.
Although no conclusive evidence has been obtained,
we believe that the above results can be rationalized if
one considers the formation of hydride nickel com-
plexes in the acidic aqueous medium.
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