C-C coupling reaction of triphenylbismuth(V) derivatives and olefins in the presence of palladium nanoparticles immobilized in spherical polyelectrolyte brushes

Article abstract of DOI:10.1002/ejic.200700825

Carbon-carbon coupling reactions were carried out by using the triphenylbismuth(V) derivatives Ph₃BiX₂ (X = O ₂CH, O₂CMe, O₂CEt, O₂CnPr, O ₂CnBu, O₂CrBu, O₂CPh, O₂CCH ₂Cl, O₂CCCl₃, O₂CCF₃) and a variety of olefins in the presence of palladium nanoparticles immobilized in spherical polyelectrolyte brushes (Pd@SPB) under mild conditions (50°C). The effects of the organobismuth derivatives and the unsaturated compounds and the influence of the ratio of solvents (THF and water) on the yield of cross-coupled products were studied. The most active organobismuth compound studied was triphenylbismuth bis(trifluoroacetate), Ph₃Bi-(O₂CCF ₃)₂. This system, which is based on the use of organobismuth compounds, allows the formation of Heck-type products without the addition of base. Time-dependent product and side-product formation is indicative of a variety of fast (relative to product formation) organobismuth decomposition pathways that lower the overall yield of the coupling reactions. In comparison to homogeneous catalyst systems used for this type of C-C coupling reaction, we only used a very low Pd loading. Wiley-VCH Verlag GmbH & Co. KGaA, 2008.

Full text of DOI:10.1002/ejic.200700825

FULL PAPER
DOI: 10.1002/ejic.200700825
C–C Coupling Reaction of Triphenylbismuth(V) Derivatives and Olefins in the
Presence of Palladium Nanoparticles Immobilized in Spherical Polyelectrolyte
Brushes
Yulia B. Malysheva,[a,b] Alexey V. Gushchin, Yu Mei, Yan Lu, Matthias Ballauff,
[b]
[c]
[c]
[c]
[a]
[a]
Sebastian Proch, and Rhett Kempe*
Keywords: Bismuth / Cross-coupling / Heck-type products / Nanoparticles / Palladium / Polyelectrolytes
Carbon–carbon coupling reactions were carried out by using
the triphenylbismuth(V) derivatives Ph BiX (X = O CH,
CtBu, CPh,
) and a variety of olefins in the
presence of palladium nanoparticles immobilized in spheri-
cal polyelectrolyte brushes (Pd@SPB) under mild conditions
2 3 2
(O CCF ) . This system, which is based on the use of
3
2
2
organobismuth compounds, allows the formation of Heck-
type products without the addition of base. Time-dependent
product and side-product formation is indicative of a variety
of fast (relative to product formation) organobismuth decom-
position pathways that lower the overall yield of the coupling
reactions. In comparison to homogeneous catalyst systems
used for this type of C–C coupling reaction, we only used a
very low Pd loading.
O
O
2
CMe,
CCH
O
2
CEt,
O
2
CnPr,
O
2
CnBu,
O
2
O
2
2
2
Cl, O CCCl
2
3
, O CCF
2
3
(50 °C). The effects of the organobismuth derivatives and the
unsaturated compounds and the influence of the ratio of sol-
vents (THF and water) on the yield of cross-coupled products
were studied. The most active organobismuth compound
(© Wiley-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim,
Germany, 2008)
3
studied was triphenylbismuth bis(trifluoroacetate), Ph Bi-
Introduction
last decade, a variety of reports have focused on the use of
palladium nanoparticles as catalyst in classic Heck coupling
reactions. At temperatures above 100 °C, molecular spe-
Heck-type chemistry is a powerful tool for carbon–car-
bon bond-forming processes. It is broadly defined as a Pd-
catalyzed C-arylation reaction of unsaturated compounds.
Normally, aryl halides are used as arylating agents in these
transformations, but other arylating agents have also been
tested for the formation of Heck-type products.[ This re-
search is directed towards finding more reactive substrates
and milder procedures that would allow for a base-free aryl-
ation. It was shown that different organometallic derivatives
[24]
cies are highly relevant and the palladium bulk material
[25]
may act as a Pd reservoir.
Classic Heck coupling reac-
tions were performed, for instance, with Pd particles on in-
[
1]
[26]
organic supports,
on chemically rather inert polymer
2,3]
[27]
[28]
supports, or stabilized in ionic liquids.
Recently, we showed that well-defined gold, platinum,
and palladium nanoparticles could be generated in a spheri-
[29–31]
cal polyelectrolyte brush and used as a catalyst.
We
[
4–8]
[9]
[10]
such as boronic acids,
arylsilanols, arylstannanes,
organoantimony,
derivatives can be used to form
report here on the use of well-defined Pd particles sup-
ported on spherical polyelectrolyte brushes (Pd@SPB) as a
catalyst for the organobismuth/olefin C–C coupling reac-
tion under mild conditions.
[
11–13]
[14]
[15–19]
aryltellurides,
organolead,
and organobismuth[
Heck-type products.
20]
Recent developments of “ligand-free” heterogeneous Pd
catalysts have provided interesting and practically impor-
tant alternatives to common ligand-assisted methodolo-
Results and Discussion
[
21]
gies.
Metal nanoparticles exhibit different properties
Triphenylbismuth dicarboxylates Ph BiX (X = O CH,
than their bulk materials and their isolated atoms. Because
of their high surface area per volume, metal nanoparticles
3
2
2
O CMe, O CEt, O CnPr, O CnBu, O CtBu, O CPh,
2
2
2
2
2
2
are ideal candidates for catalysis as well.[
22,23]
Within the
O CCH Cl, O CCCl , O CCF ; Scheme 1) were obtained
2 2 2 3 2 3
[
[
[
a] Lehrstuhl für Anorganische Chemie II, Universität Bayreuth,
5440 Bayreuth, Germany
E-mail: kempe@uni-bayreuth.de
9
b] Department of Organic Chemistry, Nizhny Novgorod State
University,
Scheme 1. Synthesis of triphenylbismuth dicarboxylates (X =
2
3 Gagarin Avenue, 603950 Nizhny Novgorod, Russia
c] Lehrstuhl für Physikalische Chemie I, Universität Bayreuth,
5440 Bayreuth, Germany
O
O
2
CH, O
2
CMe, O
CCCl
2
CEt, O
2
CnPr, O
).
2
CnBu, O
2
CtBu, O
2
CPh,
9
2
CCH Cl, O
2
2
3
, O CCF
2
3
Eur. J. Inorg. Chem. 2008, 379–383
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
379

R. Kempe et al.
FULL PAPER
Scheme 2. Synthesis of the spherical polyelectrolyte (left) and CryoTEM of Pd@SPB (right). Long chains of poly[(2-methylpropenyloxy-
2
–
ethyl)trimethylammonium chloride] were grafted onto polystyrene cores of ca. 100 nm diameter. PdCl
ions and reduction by NaBH in aqueous solution led to Pd nanoparticles with diameters of 2.6Ϯ0.5 nm that are immobilized on the
surface of the carrier particles.
4
ions were introduced as counter-
4
by the one-step reaction of triphenylbismuth with the ap-
propriate carboxylic acid in the presence of equimolar
amounts of peroxide.[
20,32]
Scheme 2 shows the structure of the spherical polyelec-
trolyte brushes (SPB) in a schematic manner: Long poly-
electrolyte chains with quaternized amino groups were
chemically grafted onto the colloidal polymer particles with
diameters of ca. 100 nm.
Scheme 3. Organobismuth Heck-type cross-coupling reaction (X =
The layer of polyelectrolyte chains attached to the sur- O CH, O CMe, O CEt, O CnPr, O CnBu, O CtBu, O CPh,
2
2
2
2
2
2
2
face of the carrier particles is very dense, that is, the contour
O
2
CCH
2
Cl, O
2
CCCl
3
, O
2
3
CCF ).
length L of the chains is much higher than their average
c
distance on the surface of the carrier particle. In this way,
We started with styrene as the coupling partner of the
a polyelectrolyte “brush” results in a system of strongly in- organobismuth compounds in the presence of Pd@SPB
teracting polymer chains inserted densely to a curved sur- (0.09 mol-%, on the basis of the corresponding organo-
face. The counterions neutralizing the charge of the poly- bismuth compound) and tetrabutylammonium bromide
electrolyte chains are nearly fully confined in the brush (TBAB) as a phase-transfer reagent in THF/H O (5:1) at
2
2
–
layer. Metal ions, for example, PdCl4 , can be immobilized 50 °C for 20 h (Table 1). Because classic Heck-type reac-
in this way and reduced to well-defined metal nanopar- tions usually require the presence of a base, we tested its
[
30]
ticles.
procedure developed by us.
metal nanoparticles generated in this way are not stabilized reactions,
Pd@SPB were synthesized by using a literature influence in the reaction. As previously observed for homo-
[29–31]
It should be noted that the geneous catalyst systems in organobismuth C–C coupling
[
20]
the addition of a base into the reaction mix-
by any surface group or other stabilizing agents (besides ture decreases the reactivity of the substrate. When tBuOK
water). Colloidal stability is brought about only by the car- was omitted from the reaction mixture, the yield of trans-
rier particles. In this way, “naked” Pd nanoparticles are stilbene increased from 3 to 7% and the yield of biphenyl
generated, and their reactivity is not impeded by any group increased from 49 to 68% (Table 1, Entries 1, 2). Tri-
bound chemically to the surface.
phenylbismuth bis(trifluoroacetate), Ph Bi(O CCF ) , was
3 2 3 2
The synthesized organobismuth compounds Ph BiX2 the most selective organobismuth compound towards the
3
were employed in C–C coupling reactions with different un- formation of the olefin C-phenylation product. trans-Stil-
saturated compounds (styrene, ethyl acrylate, butyl acrylate, bene and biphenyl were obtained in 15 and 35% yield,
acryl amide) in the presence of palladium nanoparticles im- respectively (Table 1, Entry 11). The selectivity is probably
mobilized in spherical polyelectrolyte brushes (Scheme 3). caused by the presence of the most polar carboxylic group
The reactions were carried out in water or in a mixture of in this organobismuth derivative among the studied com-
water and THF. The C-phenylation product (Heck-type pounds. The yield of trans-stilbene increased to 18% and
product) and biphenyl (homocoupled byproduct) were the yield of biphenyl decreased to 15% when triphenylbis-
found as the organic products in all cases, and benzene was muth bis(trifluoroacetate) was treated with styrene in the
found as a byproduct in some cases in trace amounts.
absence of a phase-transfer reagent (Table 1, Entry 12).
380
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© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 379–383

C–C Coupling Reaction of Triphenylbismuth(V) Derivatives and Olefins
Benzene was found in all reactions in trace amounts only. the yields of cross-coupled products were almost the same
In conclusion, the introduced catalyst system does not need independent of the nature of substrates (Table 3). The cross-
a base or a phase-transfer reagent.
coupled products were obtained in 37–52% yield. The
yields of biphenyl were 7–16%. Again, benzene was found
in nearly all reaction mixtures in trace amounts.
Table 1. Palladium-catalyzed reaction of Ph
the influence of the nature of the substituent X.
3
BiX[a]with styrene and
2
Yield[b] [%]
3 2 3 2
Table 3. Palladium-catalyzed reaction of Ph Bi(O CCF ) with dif-
Entry
Ph
3
BiX
2
ferent unsaturated compounds, and the influence of the nature of
trans-Stilbene
Biphenyl
the substrates.[
a]
1[c]
2
3
4
5
6
7
8
Ph
3
Ph
3
Ph
3
Ph
3
Ph
3
Ph
3
Ph
3
Ph
3
Ph
3
Ph
3
Ph
3
Ph
3
Bi(O
Bi(O
Bi(O
Bi(O
Bi(O
Bi(O
Bi(O
Bi(O
Bi(O
Bi(O
Bi(O
Bi(O
CH)
CH)
3
7
4
2
6
4
6
5
6
49
68
73
36
79
65
63
63
56
45
35
15
2
2
2
2
2
2
2
2
2
2
2
2
2
2
CMe)
CEt)
CnPr)
CnBu)
CtBu)
CPh)
CCH
CCCl
2
2
2
2
2
2
9
2
Cl)
2
10
11
12
3
)
2
6
15
18
CCF
CCF
3
)
)
2
[
d]
3
2
[
a] Reaction conditions: Ph
TBAB (0.1 mmol), Pd@SPB (0.09 mol-% Pd) in THF/H
0 °C for 20 h in air. [b] Yields were determined by GC: 0.3 mmol
of trans-stilbene corresponds to 100%; 0.15 mmol of Ph corre-
3
BiX
2
(0.1 mmol), styrene (0.3 mmol),
2
O (5:1) at
5
2
sponds to 100%; 0.3 mmol of benzene corresponds to 100%. [c] In
the presence of tBuOK (0.1 mmol). [d] In the absence of TBAB.
[
a] Reaction conditions: Ph
3 2 3 2
Bi(O CCF ) (0.1 mmol), unsaturated
compound (0.1 mmol), Pd@SPB (0.04 mol-% Pd) in THF/H
2
O
(
0
5:1) at 50 °C for 24 h in air. [b] Yields were determined by GC:
.1 mmol of cross-coupling product corresponds to 100%;
It was shown in the reaction of Ph Bi(O CCF ) with
3
2
3 2
styrene in the presence of Pd@SPB and without TBAB 0.15 mmol of Ph corresponds to 100%; 0.3 mmol of benzene cor-
2
(
THF/H O, 5:1; 50 °C; 20 h) that changes in the concentra- responds to 100%.
2
tion of the palladium catalyst in the range from 0.04 to
.3 mol-% Pd [on the basis of triphenylbismuth bis(trifluo-
roacetate)] did not significantly affect the yield of the C-
phenylation product. Thus, in the following experiments the
concentration of catalyst was decreased from 0.09 to
Attempts to investigate possible reaction pathways in the
particle-catalyzed version of the organobismuth C–C coup-
ling reaction were made by following one of the reactions
0
1
by H NMR spectroscopy. Possible reaction pathways of
this reaction by using molecular palladium catalysts were
0.04 mol-% Pd.
[
20]
recently described. The C-arylation reaction of ethyl ac-
rylate with tris(para-tolyl)bismuth bis(trifluoroacetate), p-
Tol Bi(O CCF ) (ratio 3:1), in the presence of Pd@SPB
The reaction of Ph Bi(O CCF ) with styrene in the pres-
3
2
3 2
ence of Pd@SPB (0.04 mol-% Pd) at 50 °C for 24 h was
3
2
3 2
carried out in THF/H O with varying ratios of these sol-
2
(0.04 mol-% Pd) at 50 °C was carried out in a mixture of
vents. The results are presented in the Table 2. It was found
that this system can be used with similar results in THF,
water, and mixture of THF and water. Addition of THF to
the reaction mixture decreases the yields of biphenyl by-
products to some extent. Benzene was found in some reac-
tions in trace amounts.
[
D ]THF/D O (5:1). The time-dependent formation of the
8
2
olefin product and the biaryl byproduct is shown in Fig-
ure 1.
Table 2. Palladium-catalyzed reaction of Ph
rene, and the influence of the ratio of solvents.
3 2 3 2
Bi(O CCF ) with sty-
[a]
Entry Solvent
THF/H
ratio
2
O
Yield[b] [%]
trans-Stilbene Biphenyl
1
2
3
4
5
THF
–
19
19
17
16
20
8
THF + H
THF + H
THF + H
2
2
2
O
O
O
5:1
2:1
1:1
–
15
15
18
35
2
H O
[
(
a] Reaction conditions: Ph
0.3 mmol), Pd@SPB (0.04 mol-% Pd) in THF/H O (5:1) at 50 °C
2
3
Bi(O
2
CCF
3
)
2
(0.1 mmol), styrene
Figure 1. Formation of the organic products in the C-arylation re-
for 24 h in air. [b] Yields were determined by GC: 0.3 mmol trans-
stilbene corresponds to 100%; 0.15 mmol Ph corresponds to
00%; 0.3 mmol benzene corresponds to 100%.
action of ethyl acrylate with p-Tol
3
Bi(O
Pd@SPB followed by H NMR spectroscopy (᭹ p-TolCH=CH-
CO Et; ᭺ p-Tol ; p-Tol = para-toluyl).
2 3 2
CCF ) in the presence of
1
2
1
2
2
In the reaction of Ph Bi(O CCF ) , which showed the
highest conversion, with different unsaturated compounds, ceeds with an initial rate of 8.9 mmoll h and the forma-
The formation of the Heck-type products (Figure 1) pro-
3
2
3 2
–1 –1
Eur. J. Inorg. Chem. 2008, 379–383
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
www.eurjic.org
381

R. Kempe et al.
FULL PAPER
tion of the bitoluyl byproduct with an initial rate of around Table 4. [Pd(cod)Cl
2
]-catalyzed (cod = 1,5-cycloctadiene) reaction
of Ph Bi(O CCF ) with different unsaturated compounds: selec-
–
1
–1
2.7 mmoll h . This means that the initial formation of the
3
2
a]
3 2
[
tivity data.
Heck-type product is around three times faster than biaryl
formation. Conversion reaches around 15% for product
and byproduct formation, and the mass balance is indica-
tive that a variety of other aryl compounds (most likely
organobismuth derivatives) must have been formed. Analy-
sis of the involved bismuth compounds (Figure 2) revealed
that the organobismuth(V) compound (starting material) is
nearly completely consumed after 150 min. The following
organobismuth(III) compounds could be identified as by-
products by NMR spectroscopy: pTol BiO CCF , pTolBi-
2
2
3
(
O CCF ) , and pTol Bi. Because organobismuth(III) com-
2 3 2 3
pounds are inactive for olefin arylation chemistry, only a
minor amount of aryl functions are available for olefin
functionalization. As a consequence, lower olefin loading
increases the yield calculated in relation to the olefin start-
ing material, as the starting olefin remains untouched to a
large amount if equimolar addition [related to the organo-
bismuth(V) derivative] took place.
[
a] Reaction conditions: Ph
compound (1.5 mmol), Pd(cod)Cl
temperature for 24 h in air. [b] Yields were determined by GC:
3
Bi(O
2
CCF
3
)
2
(0.5 mmol), unsaturated
2
(4 mol-%) in CH
3
CN at room
1
0
.5 mmol of cross-coupling product corresponds to 100%;
.75 mmol of Ph corresponds to 100%; 1.5 mmol of benzene cor-
2
responds to 100%. [c] The reaction was run for 48 h.
Conclusions
Ph Bi(O CCF ) can be used as a phenylating agent in
3
2
3 2
organobismuth C–C coupling reactions with various unsat-
urated compounds in the presence of palladium nanopar-
ticles immobilized in spherical polyelectrolyte brushes, and
the reactions can be performed in water or in a mixture of
water and THF. The reaction proceeds under mild condi-
tions. Only a small amount of the arylbismuth functionali-
ties are available for C-arylation, as rather fast formation
of catalytically inactive bismuth(III) compounds is ob-
served. In contrast to classic Heck-type reactions, these cat-
alyst systems do not need a base to obtain the olefin aryl-
Figure 2. Conversion of the starting organobismuth(V) compound ation products. The efficiency of the organobismuth C–C
followed by 1H NMR spectroscopy and yield of the organobis-
muth(III) compounds in the C-arylation reaction of ethyl acrylate
coupling reaction in comparison to the classical Heck reac-
[32]
tion is low.
It is also interesting to note that Pd@SPB
with pTol
CCF
3
)
Bi(O
2
CCF
3
)
2
in the presence of Pd@SPB [᭺ pTol
CCF ), ᭡ pTolBi(O CCF , ᭹ pTol
3
3
Bi-
Bi].
works with a much lower catalyst loading in the organobis-
muth C–C coupling reaction in comparison to homogen-
eous catalyst systems described so far. Also noteworthy is
that Pd@SPB is an efficient catalyst for classical Heck reac-
(
O
2
3
2
, o pTol
2
Bi(O
2
3
2
3
)
2
It was shown that various palladium salts introduced as
homogeneous catalysts (coordination compound) catalyze
[
33]
tions under mild conditions.
C–C coupling reactions by using triphenylbismuth dicar-
[
20]
boxylates.
Comparison of this catalyst system with
Pd@SPB reveals a high degree of similarity in terms of the
product selectivity. To solidify these similarities, we used
Experimental Section
[
Pd(cod)Cl ] as a catalyst and a catalyst loading similar to General Methods: Gas chromatographic analysis was carried out
2
with an Agilent 6890N with FID equipped with an Agilent 19091J-
those used for other homogeneous systems, and the sub-
strates were coupled with the Pd@SPB catalyst system.
Similar selectivity results were observed for both the
1
4
13, HP-5 column. H NMR spectra were measured with a Varian
Inova Unity 400 spectrometer for solutions in [D ]THF/D O (5:1).
Styrene, ethyl acrylate, butyl acrylate, acryl amide, and tetrabu-
tylammonium bromide are commercially available. Organobismuth
BiX
Synthesis and characterization of the spherical poly-
electrolyte brush and immobilization of palladium nanoparticles
8
2
[
Pd(cod)Cl ] and Pd@SPB catalyst systems (Tables 3 and
2
). Because these homogeneous catalyst systems[ produce
20]
4
compounds Ph
ods.
3
2
were prepared by the reported meth-
similar product selectivities, it is likely that particle precipi-
tation is involved in these reactions as well. Indicative of
[20,34,35]
such a similarity is also the fact that phosphane ligands can be found elsewhere.[
29–31]
All catalytic experiments were carried
poison the “homogeneous” catalyst systems.[
20]
out in pressure tubes resealable with a Teflon stopper.
382
www.eurjic.org
© 2008 Wiley-VCH Verlag GmbH & Co. KGaA, Weinheim
Eur. J. Inorg. Chem. 2008, 379–383

C–C Coupling Reaction of Triphenylbismuth(V) Derivatives and Olefins
Representative Procedure for Heck-Type Reactions: To a pressure
[17] D. V. Moiseev, V. A. Morugova, A. V. Gushchin, V. A. Do-
donov, Tetrahedron Lett. 2003, 44, 3155–3157.
tube containing Ph
3 2 3 2
Bi(O CCF ) (67 mg) in THF (10 mL) and
[
18] D. V. Moiseev, A. V. Gushchin, V. A. Morugova, V. A. Do-
donov, Russ. Chem. Bull. 2003, 52, 2081–2082.
H
2
O (2 mL) was added styrene (0.034 mL). A solution of the Pd
catalyst (solid content 0.4%, 1% Pd@SPB, 0.1 mL) was then
added, and TBAB (32 mg) was used as the phase transfer reagent.
The tube was sealed, and the reaction mixture was kept at 50 °C
for 24 h. The organic products were extracted with ether (3 mL).
The conversion was determined by GC with dodecane (0.023 mL)
as an internal standard.
[
19] D. V. Moiseev, V. A. Morugova, A. V. Gushchin, A. S. Shavirin,
Y. A. Kursky, V. A. Dodonov, J. Organomet. Chem. 2004, 689,
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2
007, 107, 133–173; b) D. Astruc, Inorg. Chem. 2007, 46, 1884–
1
Procedure for H NMR Spectroscopic Study: A mixture of pTol
3
Bi-
1894; c) J. G. de Vries, Dalton Trans. 2006, 3, 421–429; d) A.
(O
2
CF
solution in D
]THF (1 mL) and D
3
)
2
(35 mg), ethyl acrylate (0.017 mL), and the Pd catalyst
O (solid content 0.4%, 0.5% Pd@SPB, 0.1 mL) in
O (0.1 mL) was placed in an NMR tube.
Biffis, M. Zecca, M. Basato, J. Mol. Catal. A 2001, 173, 249–
2
2
74.
[D
8
2
[22] L. N. Lewis, Chem. Rev. 1993, 93, 2693–2730.
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4502.
1
The tube was sealed. The reaction was monitored by H NMR
spectroscopy every 4 min at 50 °C.
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Financial support by the Deutsch Akademische Austausch Dienst,
grant for Y. B. M., and the Deutsche Forschungsgemeinschaft,
Sonderforschungsbereich 481, Bayreuth, is gratefully acknowl-
edged. This work was supported by NanoCat, an International
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