Tail-to-tail dimerization of methyl acrylate in the presence of triphenylarsine ruthenium complexes

Article abstract of DOI:10.1080/00958972.2014.956662

Dimerization of methyl acrylate by ruthenium-based homogenous catalysts. The effect of the addition of supporting ligands on selectivity was studied. Conversion and selectivity were significantly affected by using triphenyl arsine. Possible reaction mechanism to achieve the tail to tail product was discussed. Catalytic dimerization of methyl acrylate by homogenous ruthenium catalysts was investigated. The effect of the addition of acidic additives, supporting ligands, polymerization inhibitor, and reaction conditions on the selectivity of dimerization was studied, and possible reaction mechanism was discussed. Conversion and selectivity were significantly affected by using triphenylarsine as supporting ligand. Under mild conditions, conversion up to 98% with good selectivity to tail-to-tail product was achieved.

Full text of DOI:10.1080/00958972.2014.956662

This article was downloaded by: [McGill University Library]
On: 21 February 2015, At: 11:33
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered
office: Mortimer House, 37-41 Mortimer Street, London W1T 3JH, UK
Journal of Coordination Chemistry
Publication details, including instructions for authors and
subscription information:
http://www.tandfonline.com/loi/gcoo20
Tail-to-tail dimerization of methyl
acrylate in the presence of
triphenylarsine ruthenium complexes
a
a
a
Ava Behnia , Bahareh Tamaddoni Jahromi & Ali Nemati Kharat
a
School of Chemistry, University College of Science, University of
Tehran, Tehran, Iran
Accepted author version posted online: 21 Aug 2014.Published
online: 11 Sep 2014.
Click for updates
To cite this article: Ava Behnia, Bahareh Tamaddoni Jahromi & Ali Nemati Kharat (2014) Tail-to-tail
dimerization of methyl acrylate in the presence of triphenylarsine ruthenium complexes, Journal of
Coordination Chemistry, 67:18, 3018-3025, DOI: 10.1080/00958972.2014.956662
To link to this article: http://dx.doi.org/10.1080/00958972.2014.956662
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the
“
Content”) contained in the publications on our platform. However, Taylor & Francis,
our agents, and our licensors make no representations or warranties whatsoever as to
the accuracy, completeness, or suitability for any purpose of the Content. Any opinions
and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content
should not be relied upon and should be independently verified with primary sources
of information. Taylor and Francis shall not be liable for any losses, actions, claims,
proceedings, demands, costs, expenses, damages, and other liabilities whatsoever or
howsoever caused arising directly or indirectly in connection with, in relation to or arising
out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any
substantial or systematic reproduction, redistribution, reselling, loan, sub-licensing,
systematic supply, or distribution in any form to anyone is expressly forbidden. Terms &

Conditions of access and use can be found at http://www.tandfonline.com/page/terms-
and-conditions

Journal of Coordination Chemistry, 2014
Vol. 67, No. 18, 3018–3025, http://dx.doi.org/10.1080/00958972.2014.956662
Tail-to-tail dimerization of methyl acrylate in the presence of
triphenylarsine ruthenium complexes
AVA BEHNIA, BAHAREH TAMADDONI JAHROMI and ALI NEMATI KHARAT*
School of Chemistry, University College of Science, University of Tehran, Tehran, Iran
(
Received 5 May 2014; accepted 21 July 2014)
Dimerization of methyl acrylate by ruthenium-based homogenous catalysts. The effect of the addi-
tion of supporting ligands on selectivity was studied. Conversion and selectivity were significantly
affected by using triphenyl arsine. Possible reaction mechanism to achieve the tail to tail product
was discussed.
Catalytic dimerization of methyl acrylate by homogenous ruthenium catalysts was investigated. The
effect of the addition of acidic additives, supporting ligands, polymerization inhibitor, and reaction
conditions on the selectivity of dimerization was studied, and possible reaction mechanism was
discussed. Conversion and selectivity were significantly affected by using triphenylarsine as support-
ing ligand. Under mild conditions, conversion up to 98% with good selectivity to tail-to-tail product
was achieved.
Keywords: Ruthenium complex; Methyl acrylate dimerization; Triphenylarsine; Homogenous
catalyst
1. Introduction
The selective tail-to-tail dimerization of acrylic compounds such as methyl acrylate, ethyl
acrylate, and acrylonitrile is a profitable way to synthesize an industrially important interme-
diate, adipic acid [1], which is an intermediate for nylon-66 production, fine chemicals [2],
biologically active materials [3], and pharmaceutical materials [4]. Acrylic compounds are
easily made from cheap raw materials such as propylene and light alcohols; therefore, it is
worthwhile to use these cheap compounds in organic synthesis. Numerous homogeneous
and heterogeneous catalysts have been used in these dimerizations, most of which are based
on noble metals (Rh [5], Ru [6], Pd [7]), and Ni [8]. For example, Fukuoka et al. in 1998
used [Ru(cod)(cot)] and [Ru(cod)(benzene)] as effective catalyst precursors for the tail-to-tail
dimerization of acrylonitrile under 25 atmospheres of hydrogen pressure [9]. Methyl acrylate
*
Corresponding author. Email: alnema@khayam.ut.ac.ir
2014 Taylor & Francis
©

Triphenylarsine ruthenium
3019
À
also can be smoothly dimerized at 0 °C using a nickel catalyst containing BF [10]. In 1970,
4
Barlow et al. described that palladium complexes can catalyze the linear dimerization of
methyl acrylate. They used dichlorobis(benzonitrile) palladium(II) at 113 °C for 23 h and
obtained 93% dimerization yield with a very high selectivity, but observed rapid reductive
decomposition of the palladium catalyst [11]. Pracejus et al. [12] stabilized a similar catalytic
system to prolong its lifetime by the addition of Lewis acids and AgBF for the complete
4
removal of chloride from the palladium catalyst; however, it was impractical for large scale
applications. So far, the most effective catalytic system for dimerization of methyl acrylate is
5
(
η -1,2,3-trimethylindenyl)-bis(ethene) rhodium in the presence of a proton source, that was
developed by Brookhart. This catalytic system operates between room temperature and
0 °C with high selectivity toward tail-to-tail linear dimers; however, after a while, this cata-
6
lyst is deactivated; therefore, this system requires H pressure to improve the catalyst’s life-
2
time [13]. Among precious metals, ruthenium has been studied extensively in organometallic
and coordination chemistry due to its stability and catalytic activities [14]. In 1990, phos-
phines were used as additives in Ru (CO) -catalyzed dimerization reactions in order to raise
3
12
the yield [15]. Phosphine complexes display good solubility in organic solvents and are com-
patible with metal ions in multiple oxidation states. They generally do not participate in reac-
tions, except to dissociate from the metal center, and are widely used as ligands in transition
metal catalysts [16].
In this article, we have used ruthenium complexes as catalysts for the tail-to-tail dimer-
ization of methyl acrylate; to increase the amount of tail-to-tail dimers, different types of
additives such as acids, donor ligands, and reducing agents were examined under a wide
range of reaction conditions.
2
2
. Experimental
.1. General remarks
Triruthenium dodecacarbonyl [17], dichlorotris(triphenylphosphine)ruthenium(II) [18],
chloro(pentamethylcyclopentadienyl)bis(triphenylphosphine)ruthenium(II) [19], dichloro
(
p-cymene) ruthenium(II) dimer [20], triphenylantimony, and triphenylbismuth [21] were
prepared according to literature procedures and characterized by IR spectra. Methyl acrylate,
ruthenium(III) chloride hydrate, triphenylphosphine, dodecane, and acids were purchased
from Merck and Strem chemical companies. Methyl acrylate and all solvents were dried and
distilled under argon. For monitoring reaction products, a gas chromatograph (Agilent Tech-
nologies 7890A Instrument) equipped with a HP-1 capillary column, a FID detector, and a
mass spectrometer model 5975C with a triple-axis detector was used. Yields of methyl acry-
late dimers were obtained with the use of dodecane as an internal standard. Melting points
are uncorrected and were obtained with an Electrothermal 9200 melting point apparatus.
2
2
.2. Synthesis methods
.2.1. Synthesis of triphenylarsine. Triphenylarsine was prepared according to previously
published methods for synthesis of triphenylantimony [21]. In a round-bottomed, three-
necked flask fitted with a separatory funnel, 4 g (0.165 M) of magnesium was suspended into
2
0 mL of dry diethyl ether; then 10 mL of a mixture of 26 g (0.165 M) dry bromobenzene
and 80 mL of dry diethylether was added. The remaining bromobenzene solution was added

3
020
A. Behnia et al.
during 2 h to the mixture. When the addition was finished, a solution of 9 g (0.05 M) of
freshly distilled arsenic trichloride in 30 mL of dry diethylether was added slowly through
the separatory funnel and then the mixture was heated on the steam bath for one hour. After
cooling the mixture, the reaction mixture was poured slowly, with stirring, into a mixture of
ice and water. The hydrolyzed mixture was filtered through a funnel and the residue on the
filter extracted with 30 mL of diethyl ether. The aqueous layer was separated and extracted
with diethylether. The ether layer was dried and evaporated slowly to 5 mL. After cooling,
crystals of triphenylarsine separated. Yield: 65%, m.p. 58–61 °C.
2
.2.2. Synthesis of bis(benzaldehyde)dichloro(triphenylarsine)ruthenium, ({[RuCl2
(
AsPh )(C H CHO) ]}. ({[RuCl (AsPh )(C H CHO) ]} was prepared according to
3
6
5
2
2
3
6
5
2
previously published methods with slight modifications [22]. To a solution of ruthenium
−
4
trichloride hydrate (RuCl 3H O) (0.1 g, 3.8 × 10 M) in n-butanol (10 mL, 0.1 M),
3
·
2
benzaldehyde (2 mL, 0.02 M) was added. A solution of triphenylarsine (0.6 g, 0.002 M) in
n-butanol (5 mL, 0.05 M) was added to the hot solution of ruthenium trichloride. The
resulting solution was then refluxed for 2 h. The reaction mixture was cooled overnight and
after that, a brownish-yellow crystalline compound was obtained. The compound was sepa-
rated by centrifugation and washed first with methanol and then with diethylether, and dried
under vacuum. Yield: 70%, brownish-yellow crystal, m.p. 188–192 °C, Elemental Anal.
1
Calcd for C H AsCl O Ru: C, 55.83; H, 3.66. Found: C, 55.66; H, 3.48. H NMR
3
5
25
2 2
(
CDCl , δ): 7.31–7.5 (15H, phenyl groups of AsPh ) 7.6–7.9 (8H, phenyl groups of
3
3
benzaldehyde) 9.87 (2H of aldehyde).
2
.2.3. Synthesis of chloro, cyclopentadienyl triphenylphosphine, triphenylarsine
5
5
ruthenium(II) {[(η -C H )RuCl(AsPh )(PPh )]}. A solution of [(η -C H )RuCl(PPh ) ]
5
5
3
3
5
5
3 2
−
4
−4
[
19] (0.5 g, 7 × 10 M) and AsPh (0.4 g, 1.3 × 10 M) in 60 mL benzene was heated to
3
reflux for 24 h. The resulting solution was concentrated to near dryness, the residue
extracted by CH Cl and the complex precipitated by addition of petroleum ether. It was
2
2
centrifuged and purified by recrystallization from CH Cl –petroleum ether. Yield: 75%,
2
2
orange-yellow crystal, m.p. 140 °C decom. Elemental Anal. Calcd for C H AsClPRu: C,
4
1 35
1
6
3.94; H, 4.58. Found: C, 63.8; H, 4.4. H NMR (CDCl , δ): 4.1 (5H of Cp) 7.3–7.8 (30H,
3
3
1
1
m, C H ). P{ H} NMR (CDCl , ppm): 40.1 (s, PPh ).
6
5
3
3
Table 1. Dimerization of methyl acrylate catalyzed by RuCl
3
and Ru
3
(CO)12 in the presence of acidic additives.
a
Conversion (%)
Selectivity (%)
RuCl Ru
Run
Acidic additive
Time (h)
RuCl
3
Ru
3
(CO)12
3
3
(CO)12
1
2
3
4
5
6
7
8
p-Toluenesulfonic acid
p-Toluenesulfonic acid
Methanesulfonic acid
24
48
24
48
24
48
24
48
95
68
70
47
44
31
33
27
42
24
52
41
32
20
27
12
44.2
42.7
11.4
33
20.2
22.6
52.3
53.5
66.6
24.1
33.8
47.7
33.3
63.3
38.4
Methanesulfonic acid
Trifluoromethanesulfonic acid
Trifluoromethanesulfonic acid
Trifluoroacetic anhydride
Trifluoroacetic anhydride
439
Notes: Reaction condition: catalyst (0.06 mM), methyl acrylate (22.2 mM), N-methylpyrrolidone (0.02 mM), hydroquinone (0.1 g).
a
Selectivity to tail-to-tail product.

Triphenylarsine ruthenium
3021
2.3. Catalytic reaction
All experiments were carried out three times in order to be sure about reproducibility. In a
typical experiment, a solution of 0.06 mM metal catalyst, 0.1 g hydroquinone, as polymeri-
zation inhibitor, 2 mL N-methyl-2-pyrrolidone, 0.016 mL methanol (if needed), and 2 mL
methyl acrylate were heated in a stainless steel reactor. For reactions given in Table 1,
0
.076 mM of acidic additives, and for reactions given in Table 3, 0.12 mM of supporting
ligands, were added to the reaction mixture. Decane was added as an internal standard, and
the products were analyzed by GC–mass spectroscopy.
3
. Results and discussion
Catalytic dimerization of methyl acrylate leads to a mixture of linear tail-to-tail dimers of
dimethyl hexenedioate (DHD) and branched head-to-tail dimers of dimethyl 2-methylene-
pentanedioate (MPD), as shown in scheme 1. It is clear that each catalyst system suffers
from one or more drawbacks, such as high reaction temperature, short catalyst lifetime, and
formation of branched dimers and oligomers. Selectivity to the desired product, linear tail-
to-tail dimer, is our main concern in developing an efficient catalytic system.
Various mechanisms for the catalytic dimerization of an olefinic compound with an elec-
tron-withdrawing group such as methyl acrylate [5–8] and acrylonitrile [23] were proposed.
One possible mechanism is the abstraction of a coordinated ligand to create a vacant site
for the coordination of methylacrylate followed by coupling of two methyl acrylates and
the formation of a ruthenacyclopentane. Transfer of hydride to carbon bearing the CO Me
2
group completes the cycle. Reductive elimination of the ruthenium complex gives the dimer
and catalytically active species. In scheme 2, a proposed mechanism for the linear dimeriza-
tion of methyl acrylate, which is the main product in our reactions, is shown.
We examined different kinds of acidic additives with different pK , such as para-toluene-
a
sulfonic acid, methanesulfonic acid, trifluoroacetic anhydride, and trifluoromethanesulfonic
acid, as cocatalysts with RuCl and Ru (CO) . According to Table 1, by using CF SO H,
3
3
12
3
3
which is the strongest acid (pK ~ −12) in this series, conversion reached the lowest
a
amount, in conflict with previously published work [24] where CF SO H was used in order
3
3
to activate the dihydridoruthenium(II) complex. Based on their observations, H Ru(PPh )
2
3 3
reacts with neat methyl acrylate and the catalytically active ruthenium complex is only
formed in the presence of CF SO H. We conclude that our conversion has a reverse order
3
3
with the acidity in dimerization reactions. Tembe et al. [25] observed that acid addition
completely inhibits Ru(CO) (PPh ) -catalyzed acrylate dimerization, while addition of acid
3
3 2
in similar reactions catalyzed by Ru (CO) showed only a small decrease in conversion.
3
12
An inhibitory effect was also observed by the formation of acrylic acid through hydrolysis
of acrylate esters. Acrylic acid can coordinate to ruthenium as a ligand through the carbox-
ylate group, possibly blocking the coordination sites necessary for dimerization. Because of
the hygroscopic nature of CF SO H, the presence of traces of water cannot be excluded. To
3
3
exclude the effect of moisture, CF SO H was dried over P O prior to each run; however,
3
3
2 5
the deactivation could not be completely prevented.
We observed that by using acidic cocatalyst, RuCl3 has better conversion than
Ru (CO) . Generally speaking, acidic catalysts show good conversion, at least in some
3
12
cases, but suffer from low selectivity, as shown in figure 1. Furthermore, prolonging the

3
022
A. Behnia et al.
Figure 1. Comparison of selectivity of ligands with different acids (MSA = methanesulfonic acid, PTSA =
para-toluenesulfonic acid, TFMSA = trifluoromethanesulfonic acid, TFAA = trifluoroacetic anhydride).
Scheme 1. Dimerization of methyl acrylate.
reaction time for these reactions leads to decrease in conversion probably because of the
formation of heavy byproducts.
In order to increase the conversion and selectivity to desired tail-to-tail dimer, we investi-
gated effect of addition of triphenyl pnictogen ligands (PPh , AsPh , SbPh , BiPh ) with
3
3
3
3
different electronic and steric demands in the course of the catalytic reaction. As shown in
the mechanism, free ligands will coordinate and will dissociate to open a coordination site
for approaching methyl acrylate. Therefore, the electronic and steric characters of coordinat-
ing ligands have strong impact on catalytic activity. This means by modifying electronic
character of catalyst species through coordination of ligands with good steric demands, we
can tune catalytic activities.
After testing different ruthenium complexes in conjunction with free ligands, we found
that RuCl –triphenylarsine combination displays very high activity and selectivity for the
3
dimerization of methyl acrylate, because of differences in metal-to-pnictogen bond dissocia-
tion energy and donor ability of these ligands [26]. Triphenylarsine and triphenylbismuth
exhibit lower basicities than triphenylphosphine and triphenylantimony; therefore, arsenic
compounds have poorer coordination abilities than the phosphorus and stibine analogs [27].
Triphenylarsine, which has the desired donor ability and bond energy, is found to be the
most reactive. Also the cone angles show a decrease as atom becomes heavier, and in gen-
eral, this will affect how strong it will be as a coordinated ligand; when using PPh as a
3
ligand the coordination site has been blocked more than AsPh , and this may cause dimers
3
not to reach the space around ruthenium catalyst easily.

Triphenylarsine ruthenium
3023
Scheme 2. Proposed catalytic cycles for the dimerization of methyl acrylate.
Special activity enhancement of some ruthenium complexes by using triphenylarsine is
shown in Table 2. Catalytic activity of ruthenium complexes with different electron counts
and coordination numbers was investigated. In the case of 18-electron ruthenium complexes
such as Ru (CO) , RuCl(PPh ) Cp, RuCl(Cp)(AsPh )(PPh ), and RuH CO(PPh ) , at least
3
12
3 2
3
3
2
3 3
one ligand should be dissociated to make a vacant site for coordination of methyl arylate,
so we expect lower conversion for these complexes. In the complexes containing
triphenylarsine initial triphenylarsine dissociation begins the reaction.
Table 2. Dimerization of methyl acrylate with various ruthenium complexes in the
presence of triphenylarsine.
Conversion (%)
Complex
Without AsPh
3
With AsPh
3
1
2
3
4
5
6
7
8
RuCl
Ru (CO)12
RuCl (PPh
RuCl(PPh
3
18
55
52
11
15
5
89
82
79
27
33
22
50
21
3
2
3
)
2
3
3
)
Cp
[Ru(cymene)Cl
RuH CO(PPh
RuCl(Cp)(AsPh
RuCl (AsPh )(C
2 2
]
)
3 3
2
3
)(PPh
3
)
15
7
2
3
6
H
5
CHO)
2
Notes: Reaction condition: ruthenium complex (0.06 mM), methyl acrylate (22.2 mM), N-methyl-
pyrrolidone (0.02 mM), hydroquinone (0.1 g), AsPh
time 24 h.
3
(0.12 mM), reaction temperature 145 °C,

3
024
A. Behnia et al.
For finding optimum reaction condition, further experiments were done by using different
amounts of free ligands. The results are shown in Table 3. Dimerization yield and selectiv-
ity increases in the order BiPh < SbPh < AsPh > PPh , suggesting importance of both
3
3
3
3
metal-to-pnictogen bond dissociation energy and donor ability. Effect of AsPh on RuCl is
3
3
more than Ru CO , related to close structure of ruthenium carbonyl complex.
3
12
We determined that the optimum ratio of ruthenium to AsPh is 0.12 mM. When the
3
amount of ligand was increased to 0.15 mM, the conversion and selectivity to tail-to-tail
dimers decreased significantly. For increasing conversion, we tested the experiments with
0
.12 mM AsPh in longer reaction times and found that by prolonging the reaction time,
3
the reaction is completed. As is clear from Table 3, pnictogens were very helpful supporting
ligands as they can coordinate to metal center and dissociate to create a vacant site. In other
experiments, we used diphosphine ligands such as xantphos, diphenyphosphinopropane,
and diphenylphosphinoferrocene, instead of monophosphines; these diphosphines showed
no activity for dimerization, probably strongly chelating metal center and blocking free
coordination site. Using donor ligands such as AsPh and acidic components together in
3
one reaction vessel forms insoluble salt, which may be isolated from the reaction mixture.
Ruthenium trichloride must reduce to a lower oxidation state to have reactivity in this
reaction; for this reason, we add a small amount of methanol for reduction of ruthenium. A
large amount of methanol is unnecessary because it can inhibit the reaction by competing
with free ligands and lower the selectivity; omitting methanol from the reaction mixture, no
tail-to-tail products were detected. Solvent has a striking effect on conversion and selectiv-
ity. In polar solvents, such as THF and NMP, dimerization proceeds much faster than in
nonpolar solvents such as benzene or pentane. In the former two solvents, the reactions
were complete after 24 h. Also, with changing from nonpolar to polar solvent (NMP), the
ratio of linear (DHD) to branched dimer (MPD) increases from 10 to 84%. We examined
different temperatures in the range of 90–170 °C for these catalytic experiments. Under
9
0 °C, no dimer formation occurred, and above 170 °C, the rate of production of undesired
byproducts and catalyst deactivation increased. We found 145 °C as the optimum reaction
3
Table 3. Dimerization of methyl acrylate catalyzed by RuCl in the presence of free ligands.
Run
Ligand
Metal/ligand mole ratio
Time (h)
Conversion (%)
Tail-to-tail dimers/other products
1
2
3
4
5
6
7
8
9
–
–
1
2
2
2.5
1
2
2
2.5
1
2
2
2.5
1
2
24
24
24
48
24
24
24
48
24
24
24
48
24
24
24
48
24
11
43
62
71
55
65
89
98
61
34
52
58
40
21
37
43
32
1.2
3.4
5.1
3.5
4.2
5.7
8.8
7.2
5.6
3.2
4.5
3.3
4.2
3.2
4.5
3.3
4.2
PPh
PPh
PPh
PPh
3
3
3
3
AsPh
AsPh
AsPh
AsPh
SbPh
SbPh
SbPh
SbPh
BiPh
BiPh
BiPh
BiPh
3
3
3
3
1
0
3
3
3
3
1
1
1
1
1
1
1
1
2
3
4
5
6
7
3
3
3
3
2
2.5
Notes: Reaction condition: RuCl
3
(0.06 mM), methyl acrylate (22.2 mM), N-methylpyrrolidone (0.02 mM), hydroquinone (0.1 g),
methanol (0.039 mM), reaction temperature 145 °C.

Triphenylarsine ruthenium
3025
temperature. All experiments were performed in two different reaction times, 24 and 48 h,
and conversion increased and selectivity to DHD decreased in longer reaction times.
4. Conclusion
Here, we used a new catalytic system based on ruthenium complexes to improve the yield
of tail-to-tail methyl acrylate dimerization. High conversion and good selectivity for
dimethyl hexenedioate was obtained in the presence of AsPh as supporting ligand. This
3
new catalytic system showed better selectivity than previously reported methods using
acidic additives. Up to 90% selectivity to tail-to-tail product was obtained. Further examina-
tions on dimerization of acrylonitrile by this methodology are in progress.
Acknowledgement
The authors gratefully acknowledge the financial support from the University of Tehran.
References
[
[
[
[
[
1] T. Kellersohn. Ullmann’s Encyclopedia of Industrial Chemistry, Wiley-VCH, Weinheim (1998).
2] B.A. Wexler, B.H. Toder, G. Minaskanian, A.B. Smith. J. Org. Chem., 47, 3333 (1982).
3] A. Mitra. The Synthesis of Prostaglandins, pp. 337–352, Wiley, New York (1979).
4] W.A. Nugent, F.W. Hobbs. J. Org. Chem., 48, 5364 (1983).
5] (a) T. Alderson, E.L. Jenner, R.V. Lindsey. J. Am. Chem. Soc., 87, 5638 (1965); (b) W.A. Nugent, R.J.
McKinney. J. Mol. Catal., 29, 65 (1985).
[
[
6] (a) R.J. McKinney, M.C. Colton. Organometallics, 5, 1080 (1986); (b) C.Y. Ren, W.C. Cheng, W.C. Chan,
C.H. Yeung, C.P. Lau. J. Mol. Catal., 59, L1 (1990).
7] (a) M.G. Barlow, M.J. Bryant, R.N. Haszeldine, A.G. Mackie. J. Organomet. Chem., 21, 215 (1970);
(
b) G. Oehme, I. Grassert, H. Baudisch, H. Mennenga. J. Mol. Catal., 37, 53 (1986); (c) G. Oehme, H.
Pracejus. Tetrahedron Lett., 20, 343 (1979).
[
[
8] K. Nomura, M. Ishino. J. Mol. Catal., 73, L15 (1992).
9] A. Fukuoka, T. Nagano, S. Furuta, M. Yoshizawa, M. Hirano, S. Komiya. Bull. Chem. Soc. Jpn., 71, 1409
(
1998).
[
[
[
[
10] G. Wilke. Angew. Chem. Int. Ed. Engl., 27, 185 (1988).
11] M.G. Barlow, M.J. Bryant, R.N. Haszeldine, A.G. Mackie. J. Organomet. Chem., 21, 215 (1970).
12] H. Pracejus, H.J. Krause, G. Oehme. Z. Chem., 20, 24 (1980).
13] (a) M. Brookhart, E. Hauptmann. J. Am. Chem. Soc., 114, 4437 (1992); (b) E. Hauptmann, S. Sabo-Etienne,
P.S. White, M. Brookhart, J.M. Garner, P.J. Fagan, J.C. Calabrese. J. Am. Chem. Soc., 116, 8038 (1994).
14] H.E. Toma, J.M. Malin. Inorg. Chem., 12, 1039 (1973).
15] C.Y. Ren, W.C. Cheng, W.C. Chan, C.H. Yeung, C.P. Lau. J. Mol. Catal., 59, Ll (1990).
16] N.G. Andersen, B.A. Keay. Chem. Rev., 101, 997 (2001).
17] M. Faure, C. Saccavini, G. Lavigne. Chem. Commun., 1578 (2003).
18] P.S. Hallman, T.A. Stephenson, G. Wilkinson. Inorg. Synth., 12, 238 (1970).
19] J.P. Fackler. Inorganic Syntheses, p. 79, Wiley Interscience, New York (1982).
20] J.P. Fackler. Inorganic Syntheses, p. 75, Wiley Interscience, New York (1982).
21] G.S. Hiers. Org. Synth., 1, 550 (1941).
22] R.K. Poddar, K.P. Sarma, U.C. Sarma. Polyhedron, 4, 1419 (1985).
23] K. Nomura, M. Ishino. J. Mol. Catal., 68, L5 (1991).
24] B. Patzke, R. Sustmann. J. Organomet. Chem., 480, 65 (1994).
[
[
[
[
[
[
[
[
[
[
[
[
[
25] G.L. Tembe, P.A. Ganeshpure, S. Satish. React. Kinet. Catal. Lett., 63, 151 (1998).
26] R.H. Crabtree. The Organometallic Chemistry of the Transition Metals, 3rd Edn, p. 38, Wiley Interscience,
New York (2001).
[
27] Y. Chujo. Conjugated Polymer Synthesis: Methods and Reactions, p. 229, Wiley-VCH Verlag (2010).