Ionic-tagged catalytic systems applied to the ethenolysis of methyl oleate

Article abstract of DOI:10.1016/j.catcom.2014.04.020

A novel high selective ionophilic Hoveyda-type complex for the methyl oleate ethenolysis was prepared from Grubbs first generation catalyst. Ethenolysis under classical biphasic systems in ionic liquids showed to be mass-transference limited. This drawback was successfully solved by the catalyst dispersion on high specific surface area inorganic supports through a thin layer of ionic liquids (ILs). The supported ionic liquid phase (SILP) catalyst properties were patterned by the support type, IL cation and support/IL mass ratio. The SILP prepared with the IL 1-isopentyl-3-methylimidazole hexafluorophosphate and silica showed a turnover number higher (up to 2350) than that of biphasic systems (up to 1045).

Full text of DOI:10.1016/j.catcom.2014.04.020

Ionic-Tagged Catalytic Systems Applied to the Ethenolysis of Methyl Oleate
Guilherme L.P. Aydos, B a´ rbara C. Leal, Oscar W.P. Lopez, Jairton Dupont
PII:
DOI:
Reference:
S1566-7367(14)00166-6
doi: 10.1016/j.catcom.2014.04.020
CATCOM 3888
To appear in:
Catalysis Communications
Received date:
Revised date:
Accepted date:
20 February 2014
23 April 2014
25 April 2014
Please cite this article as: Guilherme L.P. Aydos, B a´ rbara C. Leal, Oscar W.P. Lopez,
Jairton Dupont, Ionic-Tagged Catalytic Systems Applied to the Ethenolysis of Methyl
Oleate, Catalysis Communications (2014), doi: 10.1016/j.catcom.2014.04.020
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ACCEPTED MANUSCRIPT
Ionic-Tagged Catalytic Systems Applied to the Ethenolysis
of Methyl Oleate
a
b
a
b,*
Guilherme L. P. Aydos, Bárbara C. Leal, Oscar W. P. Lopez and Jairton Dupont
a
Laboratory of Catalytic Processes, Engineering Chemistry Department, UFRGS, Rua
Engenheiro Luiz Englert, s/n Porto Alegre, 90040-040 RS Brazil
b
Laboratory of Molecular Catalysis, Institute of Chemistry, UFRGS, Avenida Bento
Gonçalves, 9500 Porto Alegre, 91501-970 RS Brazil
Abstract
A novel high selective ionophilic Hoveyda-type complex for the methyl oleate
ethenolysis was prepared from Grubbs first generation catalyst. Ethenolysis under
classical biphasic systems in ionic liquids showed to be mass-transference limited.
This drawback was successfully solved by the catalyst dispersion on high specific
surface area inorganic supports through a thin layer of ionic liquids (ILs). The
supported ionic liquids phase catalysts (SILP) properties were patterned by the
support type, IL cation and support/IL mass ratio. The SILP prepared with the IL 1-
isopentyl-3-methylimidazole hexafluorophosphate and silica showed turnover number
higher (up to 2,350) than that biphasic systems (up to 1,045).
Keywords: Ethenolysis; Metathesis; Methyl Oleate; Ruthenium; Ionic Liquids
1
. Introduction
The cross-metathesis of natural derived fatty acid esters with ethylene (ethenolysis) is
one of the most attractive methods for the production of high value chemical
intermediates that have various industrial applications.[1] In fact, there has been an
increase in academic and industrial interest in transforming internal olefins derived
from seed oils to -olefins.[2, 3] In particular, there are various reports on the use of
ruthenium-based Grubbs-type metathesis catalysts for the ethenolysis of the model
substrate methyl oleate (Scheme 1).[4, 5] It is well established that these ruthenium
complexes catalyse the ethenolysis of methyl oleate under homogeneous conditions
and, in particular, Hoveyda-type catalyst precursors are highly selective for the

ACCEPTED MANUSCRIPT
formation of 1-decene and methyl 9-decenoate.[6, 7] However, these organometallic
homogeneous processes still suffer classical drawbacks, such as separation of the
products from the reaction mixture, the recovery and re-use of the catalysts, and the
substitution of volatile organic solvents.[8]
Scheme 1. Ruthenium catalysed methyl oleate metathesis.
The immobilisation of the Ru catalyst precursors on ionic liquids (ILs) is one of
most promising approaches to solve the above-mentioned basic problems.[8, 9] The
attachment of an imidazolium moiety to either a phosphine or carbene ligand (Figure
1
) is important, not only for the immobilisation of Ru-carbene complexes in ionic
liquids, but also for the stabilisation of the catalytically active species.[10-13] For
example, a continuous flow self-metathesis of methyl oleate using a supported ionic
liquid phase catalyst (SILP) prepared with ionic-tagged Grubbs–Hoveyda 2nd
generation catalyst (7) in silica using CO as a transport vector allows the use for at
2
least 10 h.[14] The efficient and selective cross-metathesis of methyl oleate with
ethylene can be achieved under mild conditions of catalyst 8 dissolved in n-1-butyl-
2
,3-dimethylimidazolium bis(trifluoromethylsulfonyl)imide IL.[15] Therefore, it is
possible to design a more stable, recyclable catalyst for the ethenolysis of natural
derived fatty acid esters. In principle, this could be achieved through supported IL
catalysts by the proper combination of the inorganic support/IL and the ionic-tagged
Ru metathesis precursor.

ACCEPTED MANUSCRIPT
Figure 1. Ru-imidazolium-tagged complexes.
Here, we report our preliminary efforts for obtaining catalytic systems (biphasic
systems and SILP) for the ethenolysis of methyl oleate based on ruthenium catalysts
containing imidazolium moieties attached to carbene derivatives.
2
. Experimental
2
.1. General Remarks
The catalyst precursor manipulations were performed in a drybox or using standard
Schlenk techniques. Ethylene Grade 2.5 (99.5%) was purchased from White Martins,
standardised Alumine 90 (CAS 134428-1) was obtained from Merck, Celite 545
(CAS 68855-54-9) was from Nuclear, and Silica Aerosil 200 (CAS 7631-86-9) was
from Degussa. Toluene, tetrahydrofuran, and dimethylformamide were distilled from
Na/benzophenone, and CH Cl was distilled from CaCl and then degassed. Hoveyda
2
2
2
catalysts 9 and 10 and Grubbs catalysts 11 and 12 (Figure 2) were obtained from
Aldrich
bis(trifluoromethylsulfonyl)imide
hexafluorophosphate (BMI·PF6),
supplier.
The
ionic
liquids
n-1-butyl-3-methylimidazolium
n-1-butyl-3-methylimidazolium
1-isopentyl-3-methylimidazolium
(BMI·NTf2),
and
hexafluorophosphate (iPMI·PF )[16] and the Ru-imidazolium-tagged carbene
6
complexes 13 and 14[12] (Figure 2) were synthesised as previously reported. Other
solvents and reagents were acquired from Aldrich and Acros suppliers, and used
without further purification.

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Figure 2. First- and second-generation Hoveyda catalysts (9 and 10), first- and
second-generation Grubbs catalysts (11 and 12) and Ru-imidazolium-tagged carbene
complexes (13 and 14).
NMR spectra were recorded on a 400 MHz Varian spectrometer at ambient probe
temperatures and referenced to internal TMS or external H PO (see NMR spectra in
3
4
the supporting information). GC analyses were performed using a Shimadzu 2010
Plus instrument equipped with a capillary column (Testek Rtx@1 - 30 m, 0.25 mm).
GC-MS data were recorded on a Shimadzu QP2010 and ESI/MS on a Micromass Q-
TOFmicro.
2
.2. Preparation of Ruthenium-Supported Ionic Liquid Phase Catalyst (Ru-SILP)
The solid supports used (alumina, celite, and silica) were exposed to a temperature of
00 °C for 2 h, cooled in a desiccator, and then maintained under vacuum for 3 h to
6
eliminate oxygen and hydroxyl groups. The pretreated solid support, IL, catalyst
precursor, and dichloromethane were added to a Schlenk and mixed vigorously for 1
min. The mixture was kept under vacuum for 30 min to completely remove of
solvent. The Ru-SILP was prepared under argon using standard Schlenk tubes
techniques just before the reactions were conducted. The prepared Ru-SILP catalysts
were identified as SILP-Complex.Support-Weight ratio IL/Support as shown in Table
1
.

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Table 1. Nomenclature of Ru-SILP.
Nomenclature
Complex/(mg) Ionic Liquid/(mg)
Support/(mg)
SILP-13.S-1
SILP-13.C-1
SILP-13.A-1
SILP-13.S-2
SILP-13.S-3
13 / (16)
13 / (16)
13 / (16)
13 / (16)
13 / (16)
13 / (16)
14 / (16)
BMI·PF / (200)
Silica / (200)
Celite / (200)
Alumina / (200)
Silica / (200)
Silica / (200)
Silica / (200)
Silica / (200)
6
BMI·PF / (200)
6
BMI·PF / (200)
6
BMI·PF / (460)
6
BMI·PF / (690)
6
i
SILP-13.S-2
iPMI·PF / (400)
6
SILP-14.S-1
BMI·PF / (200)
6
i
Ionic liquid iPMI·PF6.
2
.3. Standard Substrate
Methyl oleate to a level of 95% was obtained from double distillation of MO 75%
through a Vigreux column (25 cm) under vacuum. The distillate was characterised by
1
GC, GC-MS, and H NMR (see supporting information). Peroxyde was not detected
by Quantofix® stick test with a detection limit of 0.5 ppm. Chromatographic internal
standard (propylbenzene, 0.4393 g) was added to MO (47.8604 g), and the mixture
was degassed and then maintained in drybox for further ethenolysis reactions.
2
.4. Typical Procedure for Catalytic Tests
In a drybox, a stainless steel reactor was charged with the standard substrate (1 g, 3.2
mmol of MO) and catalyst (0.1 mol% of Ru). Next, the reactor was pressurised with
ethylene (constant pressure of 20 bar) and the reaction mixture was stirred for 24 h at
o
3
0 C. Samples were analysed by GC and the reaction products were identified by
GC-MS. When biphasic system was employed the reactor was charged also with the
IL (0.5 g). For reactions with supported catalysts the amount of SILP employed was
based on Ru content.

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3
. Results and Discussion
.1. Preliminary Studies
3
Several studies have been reported in which homogeneous ruthenium catalysts have
been successfully employed in the methyl oleate ethenolysis.[4-6] However, these
results often differ due to substrate purification, catalyst loading, and reaction
conditions. To establish the best comparative parallel, the starting point of this work
was the ethenolysis of methyl oleate with Hoveyda and Grubbs complexes (Table 2).
Complex 12 showed low selectivity for ethenolysis, even when the ethylene pressure
was increased from 8 to 20 bar (entries 1 and 2, Table 2), while complex 11 showed
high selectivity for ethenolysis (> 93%, entries 3–6, Table 2). By decreasing the
ethylene pressure from 20 to 4 bar (entries 3 and 4, Table 2), a reduction in the
conversion of MO was observed while maintaining the selectivity. The best
ethenolysis turnover number (TON ) was obtained with 45 ppm of complex 11 (entry
E
6
, Table 2).
It is clear that both Grubbs and Hoveyda first generation catalysts 11 and 9 display
higher selectivity toward ethenolysis than their second generation equivalents 12 and
0. The highest ethenolysis yield (Yield = 51%) was obtained with 1000 ppm of 9
1
E
(entry 8, Table 2). We use these first sets of experiments as basis comparison to
evaluate the ionic systems efficiency.
a
Table 2. Methyl oleate ethenolysis promoted by Hoveyda and Grubbs complexes.
b
c
d
e
f
Entry Cat./ppm Conv. (%) Yield (%) Yield (%)
Sel (%) TONE
E
H
E
g
1
12/1000
12/1000
11/1000
11/1000
11/85
54
59
39
31
25
16
75
53
46
34
7
13
38
96
98
93
95
31
97
72
206
377
304
2677
3284
233
508
2
21
38
30
23
16
23
51
3
< 1
< 1
< 1
< 1
24
h
4
5
6
7
8
11/45
10/1000
9/1000
< 1

ACCEPTED MANUSCRIPT
a
Reaction conditions: substrate (1 g), catalyst (0.1 mol%), ethylene pressure: 20 bar, 30 °C, 24 h.
b
Reaction product amounts was determined by GC. Conversion = 100 × [(initial moles of 1 - final
c
moles of 1)/initial moles of 1]. Yield of homometathesis = 100 × (moles de 4 + 5)/initial moles of 1.
d
e
Yield of ethenolysis = 100 × [(moles de 2 + 3)/2]/initial moles of 1. Selectivity = Yield of
f
g
ethenolysis/Conversion × 100. TON = Yield of ethenolysis × (initial moles of 1/moles of catalyst). 8
E
h
bar. 4 bar.
3
.2. Ethenolysis in Biphasic Systems with ionic Liquids
In agreement with previous report,[15] a significant decrease in TON was observed
E
when biphasic systems with ILs were used instead of single-phase systems under the
same conditions (compare entry 7, Table 2 versus entry 1, Table 3). We believe that
mass transfer problems, which are associated with high viscosity and poor solubility
of the reaction components on the ionic phase, are the main cause of this. In order to
pattern the influence of the ILs on the TON , BMI·NTf , and iPMI·PF were used to
E
2
6
determine the ionic phase properties (entries 2 and 3, Table 3). However, no
significant improvement was obtained by exchanging the cation. On the other hand,
–
by changing the anion to NTf , a significant decrease in the reaction conversion was
2
observed.
It is well known that the addition of organic solvents to ILs reduces the viscosity
of the mixture and, therefore, exert a significant influence on the transport properties
and on the gas solubilising capability of ionic liquids.[17-20] Furthermore, the use of
toluene was previously reported improving the catalytic efficiency of biphasic
systems of RCM.[21] Due to this, toluene was used as the co-solvent and we observed
a significant increase in the ethenolysis yield, which was accompanied with the best
selectivity (46%) for the ionic second generation catalyst 14 (entry 4, Table 3).
Similar selectivity was also achieved when the pressure was increased from 20 to 30
bar (entry 5, Table 3). For the ionic analog first generation catalyst 13, only 12% and
5
% substrate conversion was obtained when we used 1000 and 45 ppm, respectively,
but the selectivity was high.

ACCEPTED MANUSCRIPT
a
Table 3. Methyl oleate ethenolysis in biphasic systems with ionic liquids.
Conv.
YieldH
(%)
YieldE
(%)
SelE
(%)
Entry Cat.
IL
TONE
(%)
1
2
3
14
14
14
14
14
13
13
BMI·PF6
BMI·NTf2
iPMI·PF6
BMI·PF6
BMI·PF6
BMI·PF6
BMI·PF6
49
40
50
62
57
12
5
36
31
13
9
26
23
25
46
42
96
96
128
89
38
12
29
24
12
5
126
286
239
117
1045
b
4
30
c
5
29
6
< 1
< 1
d
7
a
Reaction conditions: substrate (1 g), IL (0.5 g), catalyst (0.1 mol%), ethylene pressure: 20 bar, 30 °C,
b
c
and 24 h. Reaction products amounts were determined by GC. Toluene (1 g). Ethylene pressure 30
d
bar. Catalyst loading: 45 ppm.
3
.3. Supported Ionic Liquids Phase Catalyst (SILP)
Our strategy to solve the mass transfer problems, which were clearly observed in
biphasic systems, was based on dispersing the ionophilic complexes in large area
solid supports. The performance of our complexes supported on Celite 545 and
Alumina 90 was the same (entries 1 and 2, Table 4), although the specific surface area
of the alumina was more than 20 times greater (see the supporting information). Next,
we performed the reaction using Silica Aerosil 200 as the solid support and, to our
delight, a significant increase in the catalytic activity was achieved (TON = 102
E
versus TON = 181; entries 2 and 3, respectively, Table 4). The selectivity for
E
ethenolysis was not influenced by the solid support employed. These results suggest
that the Alumina 90 pores are too small to allow dispersion of the catalyst in its
interior, or for the diffusion of the reaction products. Apparently, the external surface
area of Silica Aerosil 200, resulting from a very small particle size (12 nm), can
benefit the system.

ACCEPTED MANUSCRIPT
a
Table 4. SILP-promoted methyl oleate ethenolysis.
Conv.
YieldH
(%)
YieldE
(%)
SelE
(%)
Entry
Cat.
TONE
(%)
1
2
3
SILP-13.C-1
SILP-13.A-1
SILP-13.S-1
10
11
20
< 1
< 1
< 1
9
91
92
91
89
10
102
18
181
a
Reaction conditions: substrate (1 g), SILP (0.1 mol% of Ru), ethylene pressure: 20 bar, 30 °C, 24 h.
Reaction products amounts were determined by GC.
The effect of the amount of IL used in the preparation of SILP was evaluated next
(
Table 5). There was a significant increase in TON (181 to 381) when the IL/support
E
ratio was increased from 1:1 to 2:1 (entry 3, Table 4; and entry 1, Table 5). When a
3
:1 ratio was used, no improvement was observed (entry 2, Table 5).
Contrary to what was observed in biphasic systems, the IL cation in the SILP
systems proved to have significant importance. The ethenolysis yield increased from
8% to 49% when iPMI·PF was used (entries 3 and 4, Table 5). On the other hand,
3
6
when the amount of the complex was reduced to 45 ppm, TON (2350) was lower
E
than in the non-ionic system with 11 (TON = 3284), suggesting the poisoning of the
E
catalyst by impurities (water or phosphates, for instance) usually present in the IL or
in the support (entry 4, Table 5 and entry 6, Table 2).
a
Table 5. Influence of the IL/Support ratio in the ethenolysis of MO with 13.
Conv.
RendH
(%)
RendE
(%)
SelE
(%)
Entry
Cat.
TONE
(%)
1
2
3
SILP-13.S-2
SILP-13.S-3
42
43
52
11
< 1
< 1
< 1
< 1
38
39
49
10
90
90
93
94
381
387
i
SILP-13.S-2
491
b
i
4
SILP-13.S-2
2350
a
Reaction conditions: substrate (1 g), SILP (0.1 mol% of Ru), ethylene pressure: 20 bar, 30 °C, 24 h.
b
Reaction products amounts were determined by GC. 45 ppm.

ACCEPTED MANUSCRIPT
The SILP with the ionic second generation complex was used to study the effect
of diluting the substrate in toluene and increasing the pressure of ethylene in the
supported systems (Table 6). In the first experiments, we evaluated the performance
of the catalyst SILP-14.S-1 (TON = 369; entry 1, Table 6), and found that its activity
E
was higher than those obtained in single-phase systems with 10 and 12 (TON = 206;
E
entry 2, Table 2 and TON = 233; entry 7, Table 2, respectively) and in biphasic
E
systems (TON = 128; entry 1, Table 3) under the same conditions. Furthermore, this
E
system showed to be more active, but less selective, than the supported SILP-13.S-1.
The catalyst performance was not significantly affected by increasing the pressure
from 20 to 30 bar. In contrast to what was observed in biphasic systems, the dilution
of the substrate caused a decrease in the conversion of MO (entries 1, 2, and 3, Table
6
). The results reported in Table 6 suggest a higher propensity towards isomerisation
in the case of NHC-Ru catalysts than in the case PCy -Ru, as previously reported for
3
RCM reactions.[22, 23]
a
Table 6. Ethenolysis of MO in SILP with 14.
Entry
Cat.
Conv. (%) Rend (%) Rend (%) Sel (%) TONE
H
E
E
1
SILP-14.S-1
SILP-14.S-1
SILP-14.S-1
84
82
51
19
17
26
37
35
19
44
43
42
369
353
190
b
2
c
3
a
Reaction conditions: substrate (1 g), SILP (0.1 mol% of Ru), ethylene pressure: 20 bar, 30 °C, 24 h.
b
c
Reaction products amounts were determined by GC. 30 bar. Substrate dissolved in toluene (1:1).
4
. Conclusions
In summary, the novel, highly selective ionic ruthenium complex 13 was developed
for methyl oleate ethenolysis in ionic systems. The influence of IL anion on the
catalytic activity of ethenolysis in conventional biphasic systems with ionic liquids
–
was studied, and the best results were obtained with the anion PF . These systems
6
showed low conversions, which was clearly related to ionic phase mass transfer
problems The dispersion of the catalyst on a high specific surface area was made
.
through a thin layer of IL in silica. This methodology proved to be effective for
solving mass transfer problems. This strategy is, to our knowledge, unprecedented for
MO ethenolysis. The catalytic activity and selectivity of SILP systems were modelled

ACCEPTED MANUSCRIPT
by the IL cation, support, and support/IL mass ratio used. The best results were
obtained when the catalyst was prepared with 2:1 iPMI·PF /Silica Aerosil (SILP-
6
i
1
3.S-2 ). Its activity (TON = 491) was greater than that obtained by 13 in biphasic
E
system (TON = 117) and by non-ionic first generation Grubbs complex (TON =
E
E
3
5
77), and similar to that obtained by first generation Hoveyda complex (TON =
E
i
08). Further studies into the recyclability of the SILP-13.S-2 by using continuous
flow reactor are currently underway and will be published in due course.
Acknowledgements
The authors acknowledge CNPq and CAPES for scholarships and financial support.
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ACCEPTED MANUSCRIPT
[
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D.
Bourgeois,
A.
Pancrazi,
S.P.
Nolan, J.
Prunet,
The
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ACCEPTED MANUSCRIPT
Graphical abstract

ACCEPTED MANUSCRIPT
Highlights
A new ionic-tagged complex was prepared from Grubbs first generation catalyst.
The new complex presented high activity and selectivity to methyl oleate ethenolysis.
Nanoparticle silica was used to prepare supported ionic liquids phase catalysts.
Mass transfer properties were improved by proper ionic liquid/support ratio.
The 1-isopentyl-3-methylimidazole cation proved suitable for ethenolysis reactions.