Reactivity of 2-methyl-3-butenenitrile in the presence of catalytic amounts of various cobalt complexes in ionic liquid

Article abstract of DOI:10.1016/j.molcata.2005.11.006

The behavior of 2-methyl-3-butenenitrile (2M3BN) in the presence of catalytic amount of several cobalt complexes was evaluated. Irrespective of the nature of cobalt complexes and the experimental conditions (presence of ligand [such as P(OPh)₃ or pyridine], or/and of Lewis acid [ZnCl ₂, AlCl₃], organic solvent or ionic liquid), the product of isomerization 2-methyl-2-butenenitrile was obtained instead of the expected rearranged product 3-pentenenitrile (3PN). This result was explained by the activation of CH bond instead of CCN bond. With 3PN, the first example of a reversible cleavage of the CCN with complex derived from Co⁺ was evidenced.

Full text of DOI:10.1016/j.molcata.2005.11.006

Journal of Molecular Catalysis A: Chemical 246 (2006) 242–247
Reactivity of 2-methyl-3-butenenitrile in the presence of catalytic
amounts of various cobalt complexes in ionic liquid
Vincent Lecocqa, Catherine C. Santinia,∗, Yves Chauvina,
Jean-Marie Basseta, Jean-Christophe Gallandb
a Laboratoire de Chimie Organome´tallique de Surface, UMR 9986 CNRS—ESCPE Lyon, 43 bd du 11 Novembre 1918, F-69626 Villeurbanne Cedex, France
b Rhodia Recherches, Centre de Recherches de Lyon, Service CAT, 85 avenue des Fre`res Perret BP 62, 69192 Saint-Fons Cedex, France
Received 7 September 2005; received in revised form 3 November 2005; accepted 5 November 2005
Available online 13 December 2005
Abstract
The behavior of 2-methyl-3-butenenitrile (2M3BN) in the presence of catalytic amount of several cobalt complexes was evaluated. Irrespective
of the nature of cobalt complexes and the experimental conditions (presence of ligand [such as P(OPh)3 or pyridine], or/and of Lewis acid [ZnCl2,
AlCl3], organic solvent or ionic liquid), the product of isomerization 2-methyl-2-butenenitrile was obtained instead of the expected rearranged
product 3-pentenenitrile (3PN). This result was explained by the activation of C H bond instead of C CN bond. With 3PN, the first example of a
reversible cleavage of the C CN with complex derived from Co+ was evidenced.
© 2005 Elsevier B.V. All rights reserved.
Keywords: Pentenenitrile; Cobalt complexes; Ionic liquid
1. Introduction
Recently, we reported this catalytic rearrangement in the
presence of phosphine complexes Ni0, in biphasic ionic liq-
uid/organic solvent. Several neutral and ionic phosphines and
ionic liquids have been tested. The best results in the con-
version of 2M3BN (96%) and selectivity to 3PN (93%) were
obtained for the catalytic system associating Ni(cod)2, (m-
sulfophenyl)-diphenylphosphine sodium salt, [TPPMSNa] as
the ligand and 1-butyl-2,3-dimethylimidazolium-bis(trifluoro-
methylsulfonyl)imide [BMMIm][NTf2] as the ionic liquid, in
a biphasic ionic liquid/heptane solvent system. Partition exper-
iments proved that the catalyst was immobilized in the ionic
phase. TON (1020) and TOF (103 h−1) of the catalyst were mea-
sured [3,4]. Recycling of the catalyst is possible but leads to an
important deactivation which is related to the evolution of the
nature of the ligand by ion exchange between the cation (Na+)
of the ligand and the cation [BMMIm+] of the ionic liquid. This
exchange induces a change in the nature of the ligand, thereby
altering the nature of the catalyst and of the catalytic activity
[14].
The rearrangement of 2-methyl-3-butenenitrile (2M3BN)
into 3-pentenenitrile (3PN), the second step in the preparation
of the adiponitrile, is often chosen as a model reaction in order
to determine the catalytic performance of new ligands [1,2] or
new media, such as ionic liquid [3,4]. Besides, this conver-
sion occurring through a C CN bond cleavage (Fig. 1a), there
is a possible isomerization of 2M3BN into the side product,
2-methyl-2-butenenitrile (2M2BN) which forms via C H acti-
vation (Fig. 1a).
The nickel(0) complexes clearly give the best results and the
mechanism of the reaction of rearrangement of 2M3BN into
3PN with Ni0 catalyst (Fig. 1a) has been studied extensively
[5–8]. This mechanism is based on a Ni0 ↔ Ni2+ equilibrium.
However, some authors claimed that cobalt complexes such as
Co2(CO)8, Hg[Co(CO)4]2 and HCo[(P(OAr)3]4 {Ar = C6H5, o-
CH3C6H4} present, for this reaction, analogous results to those
of Ni0 [9–13].
Toimmobilizeacatalystintoionicliquid, thecatalystoughtto
be ionic. Another approach is to use the ionic catalytic precursor
in which the charge is on the metal center and with neutral ligand
[15–20].
∗
Corresponding author. Tel.: +33 4 72 43 18 10; fax: +33 4 72 43 17 95.
E-mail address: santini@cpe.fr (C.C. Santini).
1381-1169/$ – see front matter © 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.molcata.2005.11.006

V. Lecocq et al. / Journal of Molecular Catalysis A: Chemical 246 (2006) 242–247
243
Fig. 1. Mechanism of rearrangement in the presence of Ni0 of 2M3BN into (a) 3PN via a C CN activation; (b) 2M2BN via a C H activation.
The synthesis of (␩3allyl)Co(CO)3 has been realized using
the ionic liquid, [BMMIm][NTf2], as the solvent, instead of
ether, as described in the literature [27], allowing to isolate
and purify in only one step, (␩3allyl)Co(CO)3 by sublimation,
directly from the reaction mixture (50% yield):
In this paper, we report our attempts to realize the rearrange-
ment 2M3BN into 3PN with a series of ionic cobalt complexes in
the oxidation state Co1−, Co1+ and even Co0. The Co1− complex
is isoelectronic with Ni0. On the other hand, the cationic com-
plex Co1+ such as [(Ph2CH CHPPh2)2Co]+[ClO4]−, seems to
be a possible candidate for this reaction due to the fact it reacts
with HCN to give the cationic complex Co3+ [21]:
2. Results
2.1. Synthesis of cobalt complexes
2.2. Catalytic experiments
Several cobalt complexes (PPh3)3CoCl [22], 2,6-bis[1-(2,6-
The catalytic experiments were run as in the already pub-
lished work [3,4]. In a glove bag, a mixture of 2M3BN (distilled
over activated molecular sieves (3 A) before use), cobalt com-
diisopropylphenylimino)ethyl]pyridinecobaltmethyl,
(BIP)-
CoMe [23], 1,1,1-tris(diphenyl-phosphinomethyl)ethane cobalt
chloride, P3CoCl [24], HCo(P(OPh)3)4, NaCo(CO)4 [25],
[Co(pyridine)6][Co(CO)4]2 [26], (␩3allyl)Co(CO)2PPh3 [27]
and H[Co{P(OPh)3}4] [28,29] have been synthesized according
to the procedure available in the literature.
The reaction of (PPh3)3CoCl with Li(N(SO2CF3)2,
(LiNTf2), in the presence of bidentate p−hosphines, using
the same procedure as for the anion ClO4 [30], gave the
cationic complexes [(Ph2PCH2CH2PPh2)2Co]+[NTf2]− and
[(Ph2PCH CHPPh2)2Co]+[NTf2]−:
˚
plexes (2M3BN/[Co] = 200) and ionic liquid [BMMIm][NTf2]
(2 g) were introduced into a stirred reaction vessel or in Carousel
tubes (equipped with an external cooler to avoid incorrect mass
balance) for 3 h at 100 or 150 ◦C. The reactor was cooled down
to room temperature and the products were analyzed by gas
chromatography. Different protocols for work-up analysis were
tested. Distillation of volatile organic products under dynamic
vacuum and dilution of reaction medium with tetrahydrofuran
and direct injection into a gas chromatograph afforded good
results in terms of analysis. In all cases, at 100 ◦C as well as at
150 ◦C, no other organic compounds were detected in GC.
All cobalt complexes (PPh3)3CoCl, (BIP)CoMe, P3CoCl,
(␩3allyl)Co(CO)3, (␩3allyl)Co(CO)2PPh3 and [P3Co]+
[Co(CO)4]−, [(Ph2PCH2CH2PPh2)2Co]+[NTf2]−, [(Ph2PCH
(PPh3)CoCl + LiNTf2 + 2 Ph2PCH2CH2PPh2
EtOH
−→ [(Ph2PCH2CH2PPh2)2Co]+[NTf2]−
(PPh3)CoCl + LiNTf2 + 2 Ph2PCH CHPPh2
CHPPh2)2Co]+[NTf2]−,
HCo(P(OPh)3)4,
NaCo(CO)4,
EtOH
−→ [(Ph2PCH CHPPh2)2Co]+[NTf2]−
Co2(CO)8 and CpCo(CO)2 were tested in the catalytic condi-
tions. Irrespective of the nature of cobalt complexes and the
experimental conditions (in the presence or absence of ligand
[P(OPh)3 or pyridine], in the presence or absence of Lewis acid
[ZnCl2, AlCl3], organic solvent or ionic liquid), the rearrange-
ment of 2M3BN into 3-pentenenitrile (3PN) was not observed,
and the double bond shift product 2-methyl-2-butenenitrile
(2M2BN) was generally the main product, Table 1.
The reaction of P3CoCl with NaCo(CO)4 afforded the com-
plex [P3Co]+[Co(CO)4]− (30% yield) which was characterized
by electron spray ionization (ESI): cationic mode, 683 [P3Co+],
711 (P3Co+ + CO), 739 (P3Co+ + 2CO); and anionic mode, 171
[Co(CO)4−].

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V. Lecocq et al. / Journal of Molecular Catalysis A: Chemical 246 (2006) 242–247
Table 1
Results of the reaction of 2M3BN in the presence of catalytic amount of cobalt complexes in [BMMIm][NTf2]
Complex
T (◦C)
Conv. 2M3BN
Select. 2M2BN
Mass balance
Aspect
(PPh3)3CoCl
100
100
100
100
150
150
100
150
150
150
150
150
150
150
100
100
150
0
0
0
0
0
0
100
100
100
100
100
95
100
79
89
84
86
78
100
75
Dark green + Co metal
Dark green + Co metal
Dark green + Co metal
Dark green
Dark green + Co metal
Green-brown
Green
Green
Brown
Red
(PPh3)3CoCl + AlCl3
PPh3)3CoCl + BF3·OEt2
(PPh3)3CoCl + 5PPh3
(PPh3)3CoCl + 5PPh3
(PPh3)3CoCl + 5P(OPh)3
[(Ph2PCH2CH2PPh2)2Co]+[NTf2]−
[(Ph2PCH2CH2PPh2)2Co]+[NTf2]−
[(Ph2PCH CHPPh2)2Co]+[NTf2]−
(␩5-C5H5)Co(CO)2
(BIP)CoBr2 + ◦Zn
Co2(CO)8
Co2(CO)8 + pyridine
Co2(CO)8 + 5P(OPh)3
NaCo(CO)4
NaCo(CO)4 + 5P(OPh)3
NaCo(CO)4 + 5P(OPh)3
0
0
20
24
0
20
25
0
40
65
100
99
68
80
99
91
100
100
20
50
86
85
50
80
75
87
76
100
Orange + Co metal
Orange
Dark orange
Clear brown
Orange
92
78
94
Clear brown
Conditions: Co complex (0.036 mmol), 2M3BN (0.650 g, ca. 6.2 mmol) and [BMMIm][NTf2] (2.0 g) were stirred for 3 h at 100 or 150 ◦C. The products of the
reaction were analyzed by gas chromatography (see Section 4). (Commercial 2M3BN contains (79% 2M3BN, 12% trans-2M2BN, 6% cis-2PN and 2% trans-3PN.)
Mass balance = 100% due to the effect of the work-up, no other organic compounds have been detected.
The complex (PPh3)3CoCl was not active at 100 and 150 ◦C
even in the presence of Lewis acid and most of the com-
plex was transformed in Co particles. In the presence of an
excess of ligand (L = PPh3, P(OPh)3), the conversion in 2M2BN
was around 20%. With [(Ph2PCH2CH2PPh2)2Co]+[NTf2]− and
[(Ph2PCH CHPPh2)2Co]+[NTf2]−, the conversion of 2M3BN
occurred only above 150 ◦C. With Co2(CO)8, alone or in the
presence of pyridine or P(OPh)3, the conversion in 2M2BN
increased with temperature. With NaCo(CO)4, the conversion
of 2M2BN was total at 100 ◦C.
The stoichiometric reaction of 2M3BN with the complex
[P3Co]+[PF6]− yielded quantitatively 2M2BN. On the con-
trary, the stoichiometric reaction of [P3Co]+[PF6]− with 3-
pentenenitrile afforded a green paramagnetic compound, 2,
fully characterized as a (␩3-crotyl) complex by ESI spec-
troscopy: cationic mode 738 (P3Co((␩3-crotyl)+) and 31P NMR
(CD3NO2): 42, −27 (free ligand), −144 (PF6−). Thus, there is
activation of the C CN bond, and consequently, formation of the
Co3+ complex [P3Co3+(␩3-crotyl)(CN)][PF6]. Note that gener-
ally, the reaction of [P3Co]+[PF6]− with several diene and het-
erodiene provides [P3Co1+(␩4-diene)]+[PF6]− complexes [24].
Note that in order to compare these results with Dupont’ work
on cobalt, we reproduced rigorously the same experimental con-
ditions as those depicted in Dupont’ patent, we did not observe
any rearrangement of 2M3BN into 3PN (Table 2).
In conclusion, the rearrangement of 2M3BN into 3PN is not
observed with cobalt complexes whatever be our experimental
conditions.
At60 ◦C, 2wasspontaneouslyandquantitativelytransformed
into the starting material. In this case, the formation of conju-
gated nitrile 2PN was not observed, contrarily to the complex
[(Ph3P)3CoN2]Li, which induced isomerization of allyl cyanide
into crotonitrile [32].
On one hand, 2, in the presence of 3PN, ZnCl2 and HCN,
was decomposed (blue product P3Co2+(CN)2 derivative) and
gave 10% of valeronitrile and no dinitrile derivatives.
On the another hand, no allylcyanide was formed during
the reaction of HCN (under acetone cyanohydrin state) on
(␩3allyl)Co(CO)3 and (␩3allyl)Co(CO)2PPh3 (standard exper-
imental conditions of hydrocyanation reaction, experimental
conditions).
2.3. Stoichiometric reaction
The key step in the rearrangement of 2M3BN into 3PN
is the activation of the C–CN bond and the formation of the
(␩3allyl)Ni(CN)Ln intermediate (Fig. 1a [5–8]), while the iso-
merization of 2M3BN into 2M2BN occurs via C–H activation
(Fig. 1b). The competitive C–C and C–H bond activation reac-
tions in the isomerization of allylcyanide by Ni0 catalyst was
recently reported [6]. This study demonstrates clearly that the
C H activation induces the formation of conjugated nitrile [6].
Our results suggest that with all cobalt complexes the C H bond
activation is favored.
One example of cleavage of the C CN bond with cobalt com-
plexes is described in the case of stoichiometric reaction of alkyl
and arylnitrile with [(Ph3P)3CoN2]Li [32]. Nevertheless, with
allyl cyanide there is rearrangement into crotonitrile [32].

V. Lecocq et al. / Journal of Molecular Catalysis A: Chemical 246 (2006) 242–247
245
Table 2
Results of the catalytic rearrangement reaction of 2M3BN following the procedure depicted in Dupont’ patent
Catalyst
T (◦C)/t (h)
Amount of 3PN
present in the starting
2M3BN (%)
Amount of 3PN present in
the reactional mixture at
the end of the reaction (%)
CoCl2 (10 mmol); P(OPh)3 (40 mmol); Al (3 mmol); 2M3BN (250 mmol)
CoCl2 (10 mmol); P(OPh)3 (40 mmol); Zn (5 mmol); 2M3BN (250 mmol)
CoCl2 (10 mmol); P(OPh)3 (40 mmol); Zn (5 mmol); 2M3BN (250 mmol)
HCo(P(OPh)3)4 (5 mmol); CoCl2 (5 mmol); 2M3BN (25 mmol)
130/9
8.32
1.5
17.3a
1.5b
120/9
130/9
120/22
8.32
1.5
16.1a
1.7b
8.32
1.5
17.3a
1.9b
?
1.5
7.56a
1.5
a
Ref. [31].
Our work.
b
These results indicate that the reductive elimination to form
pentenenitrile seems to be not feasible with Co1+ precursors.
The formation of 3PN from 2 could be due to the fact that the
CN group was probably not directly bonded to the cobalt center,
as in the case of HNiL4+CN− [33]. The formation of 3PN would
be the result of nucleophilic attack of the ion CN− on (␩3-crotyl)
group. Thiswas confirmed by the fact that 3PNwasalsoobtained
when KCN was added to a solution of 2.
demonstrated that, in our standard experimental conditions,
the rearrangement of 2M3BN into 3PN, does not occur in
the presence of catalytic or stoichiometric amounts of cobalt
complexes.
Most of the results could be interpreted by an easier C H ver-
sus C C bond activation with all cobalt complexes. However,
with 3PN, the first example of a reversible cleavage of the C CN
with cationic Co1+, [P3Co]+[PF6]− was observed with the for-
mation of [P3Co(␩3-crotyl)[CN][PF6]. At 60 ◦C, the 3PN was
re-obtained, without isomerization into 2PN, probably through
a nucleophilic attack of the CN− on the crotyl group and not via
a reductive elimination as with Ni0.
3. Conclusion
Several cobalt complexes in the oxidation states −1, 0,
+1, synthesized (PPh3)3CoCl, [(Ph2PCH2CH2PPh2)2Co]+
[NTf2]−,
[(Ph2PCH CHPPh2)2Co]+[NTf2]−,
P3CoCl,
(BIP)CoMe,
(␩3allyl)Co(CO)3,
(␩3allyl)Co(CO)2PPh3,
[P3Co]+[Co(CO)4]−, HCo(P(OPh)3)4, NaCo(CO)4, commer-
cial Co2(CO)8 and CpCo(CO)2 were tested in the catalytic
reaction of rearrangement of 2M3BN. Irrespective of the
nature of cobalt complexes and the experimental conditions
(presence of ligand [P(OPh)3 or pyridine], or/and of Lewis
acid [ZnCl2, AlCl3], organic solvent or ionic liquid), only the
thermodynamically more stable 2-methyl-2-butenenitrile was
obtained instead of 3PN. The same result was obtained when
we have repeated the Dupont’ patent procedures. It has been
4. Experimental
CoCl2·6H2O, zinc powder, 3-pentenenitrile, triphenylphos-
phine, CoBr2 and MeMgBr were purchased from Aldrich and
used without further purification. Li(N(CF3SO2)2) was pur-
chased from Solvionic and used as received.
Solvents were distilled using the appropriate drying agents:
CaH2 for acetonitrile and dichloromethane, K2CO3 for chloro-
formandacetone, sodiumfortolueneandsodium/benzophenone

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V. Lecocq et al. / Journal of Molecular Catalysis A: Chemical 246 (2006) 242–247
for diethylether and tetrahydrofuran. 2-Methyl-3-butenenitrile
was purchased from Rhodia Research Center, distilled from
P2O5 and stored under argon.
NaCo(CO)4 (0.51 g, 2.6 mmol) in 10 mL of [BMMI][NTf2]. The
orange solution became green and was stirred for 12 h. It was
then distilled under vacuum to recover (allyl)Co(CO)3 (0.2 g,
50% yield) as a slightly orange liquid. 1H NMR (capillary tube):
5.47 (t, 1H), 3.61 (d, 2H), 2.72 (d, 2H). 13C (capillary tube): 205,
82, 51.
4.1. Solution NMR
1H, 13C and 31P NMR were recorded on a Bruker AC
300 MHz spectrometer. Chemical shifts were measured relative
4.7. [P3Co(η3-crotyl)(CN)][PF6]
1
to residual protons and carbons of the solvent for H and 13C,
respectively. Positive 31P chemical shifts are downfield from
external 85% H3PO4. CD2Cl2 was purchased from SDS, dis-
tilled over CaH2 and degassed before use. THF-d8 was obtained
from Aldrich and used without further treatments.
The complex P3CoCl (P3 = 1,1,1-tris(diphenylphosphino-
methyl)ethane) (0.4 g, 0.55 mmol) was dissolved in 20 mL
of THF with TlPF6 (0.192 g, 0.55 mmol). The solution was
stirred under argon and after the formation of a white pre-
cipitate, 3-pentenenitrile (0.5 mmol) was added. The reaction
medium stirred for 30 min. The solvent was removed under vac-
uum and the remaining solid extracted with dichloromethane
(2 × 10 mL). After concentration under vacuum, a green pow-
der could be isolated (0.25 g, 50% yield). Solid state 13C NMR:
4.2. 1H and 13C solid NMR
Solid state NMR spectra were recorded on a Bruker DSX-300
Spectrometer equipped with a standard 4 mm double-bearing
probe head and operating at 75.47 and 300.18 MHz for 13C and
1H, respectively. 13CNMRspectrawererecordedasfollows:30◦
pulse on 13C nuclei, and acquisition under a 80 kHz decoupling
field on protons, with 1 s recycle delay and 5 kHz spinning speed
unless otherwise specified.
167, 130 (large peak), 69, 34, 26 (large peak). Liquid state 31
P
NMR (CD3NO2): 42, −27 (free ligand), −144 (PF6−). ESI:
cationic mode, 657 (P3O2 + H+), 738 (P3Co((␩3-crotyl)+); and
anionic mode, 145 (PF6−).
4.3. Mass spectrometry
4.8. [P3Co]+[Co(CO)4]−
Mass spectra were acquired on a ThermoFinnigan LCQ
Advantage ion trap instrument, detecting positive (+) and nega-
tive (−) ions in the ESI mode. Samples (1–10 ␮g/mL in acetoni-
trile) were infused directly into the source (5 ␮L min−1) using a
syringe pump. The following source parameters were applied:
spray voltage 3.0–3.5 kV, nitrogen sheath gas flow 5–20 arbi-
trary units. The heated capillary was held at 200 ◦C. MS spectra
were obtained by applying a relative collision energy of 25–40%
of the instrumental maximum.
To a solution of P3CoCl (0.192 g, 0.26 mmol) in 10 mL of
THF NaCo(CO)4 (52 mg, 0.26 mmol) was added under argon.
The red solution was stirred for 2 h and then concentrated under
vacuum. The red solid was extracted with CH2Cl2 (3 × 5 mL)
in order to recover, after concentration under vacuum, a red
powder (70 mg, 30% yield). ESI: cationic mode, 683 (P3Co+),
711 (P3Co+ + CO), 739 (P3Co+ + 2CO); anionic mode, 171
(Co(CO)4−).
4.9. [(Ph2PCH2CH2PPh2)2Co1+][N(SO2CF3)2]
4.4. Ionic liquids
1-Butyl-2,3-dimethylimidazolium bis(trifluoromethylsulfo-
nyl)imide, [BMMIm][NTf2] has been prepared as described in
the literature. It was purified by chromatography on classical
neutral alumina (Fluka) and characterized by elemental analysis
and NMR spectroscopy [34].
To a suspension of (PPh3)3CoCl (1 g, 1.1 mmol) in 50 mL
of ethanol, the ligand Ph2PCH2CH2PPh2 (1.3 g, 3.3 mmol) and
LiNTf2 (3.7 g, 13 mmol) was added. The solution is stirred
under reflux for 3 h and then decanted at 0 ◦C. After fil-
tration, the precipitate was washed with ethanol and dried
under vacuum (1.2 g, 90% yield). ESI: cationic mode: 855
((Ph2PCH2CH2PPh2)2Co+).
4.5. Synthesis
The complexes (PPh3)3CoCl [22], 2,6-bis[1-(2,6-
diisopropylphenylimino)ethyl]pyridineCoMe [23], NaCo(CO)4
[25], (allyl)Co(CO)2(PPh3), P3CoCl [24] were synthesized
according to literature procedure.
4.10. [(Ph2PCH CHPPh2)2Co1+][N(SO2CF3)2]
The ligand diphenylphosphinoethylene Ph2PCH CHPPh2
(0.20 g, 0.5 mmol) and LiNTf2 (0.13 g, 0.5 mmol) was added
to a suspension of (PPh3)3CoCl (0.22 g, 0.25 mmol). The
reaction medium was stirred at 70 ◦C for 1 h before being
decanted at 0 ◦C. After filtration, the green precipitate was
washed with ethanol and dried under vacuum (0.22 g, 90%).
ESI: cationic mode: 851 ((Ph2PCH CHPPh2)2Co+), 455
((Ph2PCH CHPPh2)2Co+).
4.6. (η3allyl)Co(CO)3
This complex was already synthesized by the method
reported by Heck, but its preparation was greatly simplified
by using an ionic liquid. At 0 ◦C, under an argon atmosphere,
allyl bromide (0.2 mL, 2.4 mmol) was added to a solution of

V. Lecocq et al. / Journal of Molecular Catalysis A: Chemical 246 (2006) 242–247
247
4.11. Catalytic experiments and analysis
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In a typical reaction, 0.036 mmol of cobalt complex (1 eq.),
0.650 mg of 2M3BN (220 eq.) and 2.0 g of BMMImNTf2 were
mixed under argon. The reaction medium was then heated for
3 h at 100 or 150 ◦C, and then cooled in liquid nitrogen.
Work-up: butylbenzene (100 mg) was added to the reac-
tion mixture as an internal standard, reaction medium was then
diluted with 10 mL of THF and a portion was directly injected
into a gas chromatograph.
Analyses: The products were quantitatively analyzed by
gas chromatography (HP6890 equipped with a TCD detec-
tor, Stabilwax-DA (polyethyleneglycol) column (L = 30 m,
φint = 0.53 mm, film thickness = 1 ␮m).
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