Study of homo- and cross-coupling competition in the reaction of triarylbismuth(V) dicarboxylates with methyl acrylate in the presence of a palladium catalyst

Article abstract of DOI:10.1016/j.jorganchem.2005.04.051

Triarylbismuth(V) derivatives Ar₃Bi(O₂CR)₂ (Ar = Ph, m-Tol, p-Tol; R = H, Me, Et, n-Bu, t-Bu, n-C₅H ₁₁, CF₃, CH₂Cl, CCl₃, Ph) were prepared in good to excellent yields by reaction of Ar₃Bi with equimolar amounts of t-BuOOH in the presence of an acid. These compounds were tested in the C-arylation reaction of methyl acrylate, as a model substrate, in the presence of palladium catalyst (4 mol%). It was found that triphenylbismuth dicarboxylates are very active phenylating agents under mild conditions (20 °C). The effect of the carboxylic group, the effect of the nature of the palladium catalyst and the effect of oxygen on the reactivity of the organobismuth compounds and on the selectivity of the C-arylation reaction were studied. Methyl cinnamate, the C-phenylation product, and biphenyl, the homo-coupling by-product, were obtained in all cases. Triphenylbismuth divalerate Ph₃Bi(O₂CBu)₂ is the most reactive compound among the triphenylbismuth dicarboxylates studied.

Full text of DOI:10.1016/j.jorganchem.2005.04.051

Journal of Organometallic Chemistry 690 (2005) 3652–3663
www.elsevier.com/locate/jorganchem
Study of homo- and cross-coupling competition in the reaction
of triarylbismuth(V) dicarboxylates with methyl acrylate
in the presence of a palladium catalyst
a,
a
b
Dmitry V. Moiseev *, Yulia B. Malysheva , Andrey S. Shavyrin ,
b
Yury A. Kurskii , Aleksey V. Gushchin
a
a
Department of Organic Chemistry, Nizhny Novgorod State University, 23 Gagarin Avenue, 603950 Nizhny Novgorod, Russia
b
G.A. Razuvaev Institute of Organometallic Chemistry, Russian Academy of Sciences, GSP-445, 49 Tropinin Street, 603950 Nizhny Novgorod, Russia
Received 30 November 2004; received in revised form 19 April 2005; accepted 20 April 2005
Available online 24 June 2005
Abstract
Triarylbismuth(V) derivatives Ar3Bi(O2CR)2 (Ar = Ph, m-Tol, p-Tol; R = H, Me, Et, n-Bu, t-Bu, n-C5H11, CF3, CH2Cl, CCl3,
Ph) were prepared in good to excellent yields by reaction of Ar3Bi with equimolar amounts of t-BuOOH in the presence of an acid.
These compounds were tested in the C-arylation reaction of methyl acrylate, as a model substrate, in the presence of palladium cat-
alyst (4 mol%). It was found that triphenylbismuth dicarboxylates are very active phenylating agents under mild conditions (20 °C).
The effect of the carboxylic group, the effect of the nature of the palladium catalyst and the effect of oxygen on the reactivity of the
organobismuth compounds and on the selectivity of the C-arylation reaction were studied. Methyl cinnamate, the C-phenylation
product, and biphenyl, the homo-coupling by-product, were obtained in all cases. Triphenylbismuth divalerate Ph3Bi(O2CBu)2 is
the most reactive compound among the triphenylbismuth dicarboxylates studied.
Ó 2005 Elsevier B.V. All rights reserved.
Keywords: Bismuth(V); Arylation; Palladium; Homo-coupling; Cross-coupling
1. Introduction
Ar4SbX (X = Hal, O2CR) perform the palladium-cata-
lyzed C-phenylation reaction of unsaturated compounds
with transfer of one aryl group of the antimony deriva-
tive [4]. However, in the presence of peroxide three aryl
groups are involved in the reaction [1].
In continuation of our research, we studied the appli-
cation of triarylbismuth dicarboxylates in the C-phenyl-
ation reaction. Due to the low energy of the C–Bi bond
the organobismuth derivatives are highly reactive and
could be applied for a new C–C bond formation under
very mild conditions. Organobismuth compounds are
currently receiving much interest [5]. There are several
examples of palladium-mediated conversions of a C–Bi
bond into a C–C bond. Cross-coupling have been ob-
served in the reaction of Ar3Bi with acyl chloride [6],
aryl halides and triflates [7], allyl halides [8] and in the
Application of heteroatom-containing compounds in
organic synthesis is a rapidly growing area of research.
Recently, we showed that some types of organoanti-
mony(V) derivatives are efficient agents in the palla-
dium-catalyzed C-arylation reaction of unsaturated
compounds under mild conditions. Triarylantimony(V)
dicarboxylates Ar3Sb(O2CR)2 in the presence of PdCl2
arylate selectively unsaturated compounds with involve-
ment of one aryl group of the antimony derivative under
inert atmosphere and of two aryl groups in the presence
of oxygen [1–3]. Tetraarylantimony(V) derivatives
*
Corresponding author. Tel.: +7 831 2337865; fax: +7 831 2658592.
E-mail address: moisdv@mail.nnov.ru (D.V. Moiseev).
0022-328X/$ - see front matter Ó 2005 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2005.04.051

D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
3653
reaction of organobismuth dialkoxides with aryl or alke-
nyl triflates and aryl halides [9,10]. Pentavalent triaryl-
bismuth compounds Ar3BiX2 (X = Hal, OAc) have
been used in the palladium-catalyzed cross-coupling
reaction with hypervalent iodonium salts at room tem-
perature [11]. The homo-coupling of organobismuth
compounds has also been studied [6,12]. Triarylbismuth
has been used in the carbonylation reaction as well [13].
Arylation of vinyl epoxides, diol acetonides and diol
carbonates has been performed with both triarylbis-
muth(III) and triarylbismuth(V) dichloride or carbonate
[14]. Several types of organobismuth(III) compounds
have been tested in Heck-type reactions [15–17]. Bis-
muth ylides have been used to study a homo- and
cross-coupling competition [18].
derivatives 6a–c, the homo-coupling products, were
found in all cases. In some cases formation of aromatic
hydrocarbons (7a–b) also occurred (Scheme 2).
The nature of the palladium catalyst as well as the
presence of additional ligands affect the yields of the
reaction products (Table 1). In all cases the main reac-
tion product is biphenyl 6a. Among the catalysts studied
in the C-phenylation reaction of 4 with triphenylbismuth
dipropionate Ph3Bi(OEt)2 1c PdCl2 is the most effective
toward the formation of the cross-coupling product 5a
(53%) with a 5a/6a ratio of 0.5 (Table 1, entry 1). The
100% yield of methyl cinnamate or benzene relates to
the involvement of one phenyl group of the starting
organometallic compounds, whereas the 100% yield of
biphenyl relates to the involvement of two phenyl
groups. Another palladium salt Pd(OAc)2 shows the
same activity in terms of phenyl group involvement
(275%), but the selectivity of the C-phenylation process
(or the 5a/6a ratio) is lower (Table 1, entry 2) than that
obtained with PdCl2. The presence of triphenylphos-
phine in the coordination sphere of palladium does
not affect the homo-coupling reaction (Table 1, entries
3 and 4). At the same time, the yield of 5a decreases dra-
matically, and in the case of large excess of Ph3P ligand
the cross-coupling reaction is stopped completely (Table
1, entry 4). Under these conditions, the Ph3P ligands
bind too strongly to the palladium center to allow the
exchange reaction with 4 to produce 5a.
2. Results and discussion
2.1. Synthesis of Ar3BiX2
The organobismuth dicarboxylates Ar3Bi(O2CR)2
were obtained in moderate to good yields by the one-
step reaction of triarylbismuth with the appropriate car-
boxylic acid in the presence of equimolar amounts of
peroxide (Scheme 1) [19].
2.2. Reaction of Ph3BiX2 with methyl acrylate at 50 °C
The use of diphosphines such as dppm [bis(diph-
enylphosphino)methane], dppe [1,2-bis(diphenylphosph-
ino)ethane], dppp [1,3-bis(diphenylphosphino)propane],
dppb [1,4-bis(diphenylphosphino)butane] also affects
the reaction. In the case of dppm the total yield of the
reaction is the highest (300%) and corresponds the full
involvement of all phenyl groups of the starting com-
pound 1c (Table 1, entry 5). However, the selectivity
of the cross-coupling process is lower (0.34) than that
obtained using the PdCl2 catalyst. The palladium cata-
lyst with dppe ligand has the lowest activity. Methyl cin-
namate 5a and biphenyl 6a were obtained in 9% and
11% yield, respectively (Table 1, entry 7). However,
increasing the number of carbon atoms in the backbone
chain of the diphosphine leads to higher activity of the
catalyst. In the case of dppp and dppb the total involve-
ment of phenyl groups under these conditions reaches
185% and 235%, respectively (Table 1, entries 8 and 9).
Such effect of the diphosphines is probably caused by
the strain imposed by the respective bite-angles upon
chelation of the phosphines to the palladium atom. In
the case of dppe (bite-angle 85° [20–22]) the most stable
palladium complex is formed. This complex is stable en-
ough under these conditions to stop a catalytic cycle
(Table 1, entry 7). In the case of dppm, the very strained
bite-angle (72°) [20,21] causes the dissociation of one
phosphorus atom. This allows a molecule of 4 to be
coordinated to the palladium atom (Scheme 3, A). When
The organobismuth(V) dicarboxylates were tested in
the Heck-type C-arylation reaction of methyl acrylate
4, which was used as a model unsaturated substrate
for the cross-coupling reaction, in the presence of cata-
lytic amounts of various palladium complexes. To com-
pare the reactivity of the organobismuth compounds
with that of the corresponding organoantimony deriva-
tives the reactions were initially carried out under the
same conditions used for the antimony compounds: in
acetonitrile at 50 °C for 3 h, under air with ratio between
[Bi(V)], 4 and [Pd] of 1:3:0.04. The trans-arylation prod-
ucts, the cinnamic acid derivatives 5a–c, and the biaryl
rt
Ar3BiX2
+
t-BuOH + H2O
Ar3Bi + 2 HX
+ t-BuOOH
24 h
1 Ar = Ph
1a X = O2CH
1b X = O2CMe
1c X = O2CEt
1d X = O2CBu-n
1e X = O2CBu-t
88%
94%
80%
70%
62%
1f X = O2CC5H11-n 44%
1g X = O2CCF3 40%
1h X = O2CCH2Cl 55%
1i X = O2CCCl3
1j X = O2CPh
2a X = O2CBu-t
3a X = O2CEt
30%
87%
41%
65%
2 Ar = p-Tol
3 Ar = m-Tol
Scheme 1.

3654
D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
[Pd]
Ar3BiX2
Ar CH=CH CO2Me
+
Ar Ar
ArH
+
CH2 CH CO2Me
+
5a Ar = Ph
5b Ar = p-Tol
5c Ar = m-Tol
6a Ar = Ph
6b Ar = p-Tol 7b Ar = p-Tol
6c Ar = m-Tol or m-Tol
7a Ar = Ph
4
Scheme 2.
was observed. The use of the xantphos ligand (111°)
[20] decreased the selectivity of the C-phenylation reac-
tion significantly. Methyl cinnamate 5a and biphenyl
6a were found in 32% and 121% yield, respectively (Ta-
ble 1, entry 11). Thus, PdCl2, employed alone, appears
to be the most efficient catalytic species for this C-
phenylation reaction.
Table 1
Palladium catalyzed reaction of Ph3Bi(O2CEt)2 1c with methyl acrylate
4 at 50 °C: influence of the nature of the catalysta
Entry [Pd]
Yieldsb(%)
5a/6a ratio RPh (%)
5a 6a
7a
1
2
PdCl2
Pd(OAc)2
53 105
29 123 tr
6
0.50
0.24
0.06
–
269
275
229
208
300
275
31
Under the conditions used in the present study all tri-
phenylbismuth dicarboxylates are reactive in the homo-
and cross-coupling processes (Table 2). The selectivity of
the reaction depends on the nature of the carboxylic
group. The highest yield of 5a (85%) with good selectiv-
ity (1.13) was observed in the case of triphenylbismuth
dibenzoate Ph3Bi(O2CPh)2 1j (Table 2, entry 5). How-
ever, benzene 7a was also obtained in high yield
(54%). In the cases of other derivatives of strong acids,
such as the formate 1a and the triflouroacetate 1g, ben-
zene was also found in high yield (59% and 41%, respec-
tively) (Table 2, entries 1 and 7). Simultaneously, the
selectivity of the C-phenylation reaction was high (1.52
and 1.07, respectively). The high yield of 7a can be ex-
plained by dephenylation of the organobismuth(III)
derivatives formed in the reaction with a strong acid
generated during the course of the reaction. Indeed,
addition of triethylamine as a base into the reaction mix-
ture stopped the formation of benzene. However, unfor-
tunately, the selectivity of the reaction concomitantly
decreased dramatically from 1.13 to 0.25 (Table 2, en-
tries 5 and 6). The divalerate 1d showed similar activity
to that of 1c (Table 2, entries 3 and 4). In the case of the
3
Pd(Ph3P)2Cl2
PdCl2 + 6 Ph3P
PdCl2 + dppm
PdCl2 + 2 dppm
PdCl2 + dppe
PdCl2 + dppp
PdCl2 + dppb
PdCl2 + BINAP
6
109
104
5
0
5
4
4
tr
5
43 126
0.34
0.05
0.82
0.18
6
7
9
132
7
11 tr
82
8
15
26
49
6
185
235
262
285
9
98 13 0.27
92 29 0.53
10
11
a
PdCl2 + Xantphos 32 121 11 0.26
The reactions were performed in CH3CN at 50 °C for 3 h, under air
with ratio between [Bi], 4 and [Pd] of 1:3:0.04.
b
Yields were determined by GLC.
using a twofold excess of dppm this free coordination
site is occupied by the second phosphine (Scheme 3, B)
and the C-phenylation reaction is stopped (Table 1, en-
try 6). Diphosphines such as dppp and dppb (bite-angle
95° and 99° [21,22], respectively) also form strained and
unstable complexes.
Ligands possessing a rigid structure like BINAP and
xantphos were also tested. The BINAP ligand (92°) [20]
gave the highest yield of 5a (49%). The selectivity of the
C-phenylation reaction was also high (0.53) (Table 1, en-
try 10). Besides, the highest yield of benzene 7a (29%)
CO2Me
P
P
Ph
P
P
Ph
Ph
X
CO2Me
Pd
Pd
Pd
X
P
X
P
P
P
A
B
PPh2
PPh2
O
PPh2
Ph2P
BINAP
Xantphos
Scheme 3.

D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
3655
Table 2
PdCl2 catalyzed reaction of Ph3BiX2 with methyl acrylate 4 at 50 °C:
influence of the nature of the substituent Xa
50 °C, 3 h, under air), generally, more than two phenyl
groups are involved in the palladium-mediated pro-
cesses. The phosphine ligands and the carboxylic group
of the bismuth(V) derivative affect the competition be-
tween these two main processes. It was anticipated that
these effects could be observed more clearly under
milder conditions to understand a mechanism of the
process, therefore investigations on the same reactions
at room temperature were carried out, and the results
are discussed in the following section.
Entry
X
Yieldsb (%)
5a/6a ratio
RPh (%)
5a
6a
46
7a
1
O2CH (1a)
O2CMe (1b)
O2CEt (1c)
O2CBu-n (1d)
O2CPh (1j)
O2CPh (1j)
O2CCF3 (1g)
Cl
70
26
53
57
85
31
59
72
59
3
1.52
0.20
0.50
0.57
1.13
0.25
1.07
1.41
221
283
269
275
289
287
210
212
2
127
105
100
75
3
6
4
18
54
4
5
6c
126
55
7
41
18
8d
a
51
2.3. Reaction of Ph3BiX2 with methyl acrylate at room
temperature
The reactions were performed in CH3CN at 50 °C for 3 h, under air
with ratio between [Bi], 4 and [Pd] of 1:3:0.04.
b
Yields were determined by GLC.
Indeed, in the reaction of Ph3Bi(O2CPh)2 1j, which
showed the highest reactivity at 50 °C, with 4 at room
temperature for 3.5 h the total involvement of phenyl
groups in the reaction was 120% with almost the same
selectivity (1.16) (Table 3, entry 1). When the reaction
was performed for 24 h the total involvement increased
to 227%. The yields of 5a and 6a were similar to those
obtained at 50 °C (80% and 71%, respectively) (Table 3,
entry 2). This reaction is less selective in the presence
of other palladium catalyst. Palladium species such as
Pd2(dba)3 and Pd(OAc)2 showed the same activity in
the production of 5a (70%) but different selectivity
(0.93 and 0.78, respectively) (Table 3, entries 3 and 4).
In the case of Li2PdCl4 the products 5a and 6a were
obtained in 58% and 84% yield, respectively (Table 3,
entry 5). Addition of the phosphine ligands to the reac-
tion decreases the yield of 5a. In the case of dppm the
yield of methyl cinnamate 5a decreased from 80% in
the absence of the ligand to 45%. At the same time the
yield of 6a increased from 71% to 87% (Table 3, entries
6 and 2). The addition of Ph3P stops the reaction
c
Addition of base Et3N in amount of 1–1 mol of organobismuth
compound.
d
PhCl was found in 20% yield.
diacetate 1b the lowest selectivity was observed (0.20).
Biphenyl 6a was the main product of the reaction
(127%) (Table 2, entry 2). It was surprising that triphe-
nylbismuth dichloride Ph3BiCl2 showed a high reactivity
as well, unlike Ph3SbCl2, which was completely inactive
in this reaction [2]. The C-phenylation product 5a was
obtained in 72% yield with good selectivity (1.41) (Table
2, entry 8). PhCl was also found as a by-product of the
reaction in 20% yield. Thus, triphenylbismuth dibenzo-
ate Ph3Bi(O2CPh)2 1j is the best reagent among those
studied for the C-phenylation reaction under these
conditions.
Thus, all the organobismuth(V) dicarboxylates exhib-
ited a very high reactivity toward both the palladium
catalyzed C-phenylation reaction and the homo-
coupling process. Under these conditions (CH3CN,
Table 3
Palladium catalyzed reaction of Ph3Bi(O2CR)2 (R = Ph or Et) with methyl acrylate 4 at room temperature: influence of the nature of the catalysta
Entry
Triphenylbismuth compound
[Pd]
Yieldsb (%)
5a/6a ratio
RPh (%)
5a
6a
38
7a
1c
2
3
4
5
6
7
Ph3Bi(O2CPh)2
PdCl2
PdCl2
44
80
70
70
58
45
0
0
5
1.16
1.13
0.93
0.78
0.69
0.52
–
120
227
220
250
226
225
0
71
75
90
84
87
0
Pd2(dba)3
Pd(OAc)2
Li2PdCl4
PdCl2 + dppm
Pd(Ph3P)2Cl2
tr
tr
tr
6
0
8
9d
10
11
12
a
Ph3Bi(O2CEt)2
PdCl2
58
4
96
104
88
12
12
0
0.60
0.04
0.14
0.76
0.65
262
224
188
278
300
Pd(Ph3P)2Cl2
PdCl2 + dppm
PdCl2 + BINAP
PdCl2 + Xantphos
12
74
74
97
111
10
4
The reactions were performed in CH3CN at room temperature for 24 h, under air with ratio between [Bi], 4 and [Pd] of 1:3:0.04.
Yields were determined by GLC.
Reaction time was 3.5 h.
b
c
d
Reaction time was 70 h.

3656
D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
completely (Table 3, entry 7). Benzene 7a was found in
negligible amount in all reactions of 1j at room temper-
ature, unlike in the reaction at 50 °C, where it was
obtained in 54% yield (Table 2, entry 5).
cross- and homo-coupling products were obtained in
92% and 103% yield, respectively (Table 4, entry 4).
The bismuth derivatives containing less carbon atoms
in the carboxylic group showed lower reactivity. This
reactivity decreased in the order: 1d (298%) > 1c
(262%) > 1b (248%) > 1a (170%), and the yields of 5a
decreased correspondingly (92%, 58%, 34% and 38%,
respectively). (Table 4, entries 1–4). However, the yields
of 6a did not change significantly in the cases of the
valerate 1d, propionate 1c or acetate 1b. Only in the case
of the formate 1a the yield decreased to 35%, but the
yield of 7a increased considerably (62%) (Table 4, entry
1). The reactivity of organobismuth compounds
decreases also when derivatives containing more bulky
carboxylic groups, Ph3Bi(O2CBu-t)2 1e or Ph3Bi(O2C-
C5H11-n)2 1f, are used. In the case of 1e, methyl cinna-
mate 5a and biphenyl 6a were obtained in 85% and
83% yield, respectively (Table 4, entry 5). In the case of
1f the corresponding yields were 72% and 91%, respec-
tively (Table 4, entry 6). The presence of electron-with-
drawing atoms in the carboxylic group also decreases
the reactivity of the organobismuth compound. The
involvement of phenyl groups decreases in the order:
acetate 1b (248%) > monochloroacetate 1h (203%) > tri-
chloroacetate 1i (39%) (Table 4, entries 2, 9 and 10).
However, at the same time the selectivity of the C-pheny-
lation reaction increases from 0.32 in the case of 1b to
1.40 in the case of 1i. The triphenylbismuth bis(triflouro-
acetate) Ph3Bi(O2CCF3)2 1g also showed low reactivity.
The products 5a and 6a were obtained in 28% and 23%
yield, respectively (Table 4, entry 8). Thus, the nature
of the carboxylic group has a strong effect on the reactiv-
ity of the organobismuth compounds and on the selectiv-
ity of the C-phenylation reaction. Triphenylbismuth
divalerate Ph3Bi(O2CBu-n)2 is the most effective among
triphenylbismuth(V) dicarboxylates studied in the reac-
tion. The organobismuth derivatives containing the
To compare the activity of the palladium catalysts at
room temperature and at 50 °C a number of reactions
were carried out with the triphenylbismuth dipropionate
Ph3Bi(O2CEt)2 1c. PdCl2 did not show significant
changes in activity and selectivity. The yields of 5a and
6a were 58% and 96%, respectively (Table 3, entry 8).
However, Ph3P reduces the activity more effectively at
room temperature than at 50 °C. Only after 3 days
biphenyl 6a was obtained as the main product in 104%
yield. 5a was obtained in 4% yield (Table 3, entry 9).
In the case of dppm the yield of 5a decreased from
43% at 50 °C to 12% at room temperature. The selectiv-
ity of the C-phenylation reaction also decreased from
0.34 to 0.14 (Table 1, entry 5, Table 3, entry 10). This
fact can be explained by invoking higher stability of
the bidentate palladium complex under milder condi-
tions. The use of the rigid diphosphines such as BINAP
or xantphos leads to improvement in the yield of 5a and
in the selectivity of the C-phenylation process. In the
case of the BINAP ligand the yield of 5a increased from
49% to 74%, the yield of 6a almost did not change and
was 97% (Table 1, entry 10, Table 3, entry 11). In the
case of the xantphos ligand the yield of 5a increased
more significantly, from 32% to 74%. The yield of 6a de-
creased slightly (Table 1, entry 11, Table 3, entry 12).
The carboxylic group affects the reactivity of organo-
bismuth compounds and the selectivity of the C-phenyla-
tion process. To understand this effect triphenylbismuth
dicarboxylates were tested in the C-phenylation reaction
at room temperature. The triphenylbismuth divalerate
Ph3Bi(O2CBu-n)2 1d is the most reactive triphenylbis-
muth derivative among those studied. The total involve-
ment of phenyl groups in this case is 298%. The
Table 4
PdCl2 catalyzed reaction of Ph3BiX2 with methyl acrylate 4 at room temperature: influence of the nature of the substituent Xa
Entry
X
Yieldsb (%)
5a/6a ratio
RPh (%)
5a
6a
7a
1
2
O2CH (1a)
38 (20)c
34 (15)
58 (39)
92 (53)
85 (54)
72
35 (25)
107 (52)tr (14)
96 (69)
103 (69)
83 (45)
91
62 (51)
0.32 (0.28)
12 (16)
tr (28)
5 (31)
5
1.09 (0.80)
248 (133)
0.60 (0.57)
0.89 (0.77)
1.02 (1.20)
0.79
170 (121)
O2CMe (1b)
O2CEt (1c)
O2CBu-n (1d)
O2CBu-t (1e)
O2CC5 H11-n (1f)
O2CPh (1j)
O2CCF3 (1g)
O2CCH2Cl (1h)
O2CCCl3 (1i)
Cl
3
262 (193)
298 (219)
253 (175)
259
4
5
6
7
80 (23)
28 (20)
53 (22)
14 (15)
54
71 (36)
23 (45)
57 (52)
10 (14)
39
5 (31)
0 (3)
1.13 (0.64)
1.22 (0.44)
0.93 (0.42)
1.40 (1.07)
1.38
227 (126)
74 (113)
203 (181)
39 (51)
227
8
9
33 (53)
5 (8)
10
10
11d
a
The reactions were performed in CH3CN at room temperature for 24 h, under air with ratio between [Bi], 4 and [Pd] of 1:3:0.04.
Yields were determined by GLC.
b
c
Yields of products in the reaction under argon are indicated in brackets.
Methyl hydrocinnamate and PhCl were found in 21% and 4% yield, respectively.
d

D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
3657
stronger electron-withdrawing carboxylic groups have
the lowest reactivity. The selectivity of the C-phenylation
reaction is higher at room temperature than that at 50 °C.
The effect of the solvent was studied in the reaction of
the valerate 1d with 4 (1:3). Acetonitrile has a determi-
nant effect on the yield of the products (Table 4, entry
4). When DMF or THF were used the yield of 5a de-
creased dramatically (31% and 23%, respectively). At
the same time, however, the yields of 6a are similar to
those in acetonitrile, 84% and 100%, respectively. The
yields of both products become lower in benzene,
CH2Cl2 or hexane: 6–17% for the C-phenylation prod-
uct, 34–78% for the biphenyl. Thus, acetonitrile is the
best solvent for the C-phenylation reaction with the
organobismuth compounds.
Oxygen plays an important role in the C-arylation
reaction of olefins with triarylantimony dicarboxylates
[2]. To establish the effect of oxygen on the C-phenyla-
tion process with triphenylbismuth dicarboxylates some
reactions were carried out under inert atmosphere. The
results of these reactions are shown in brackets in Table
4. The reactivity of the organobismuth compounds and
the selectivity of the C-phenylation reaction decreased
significantly in almost all cases. The reactivity of the tri-
phenylbismuth dicarboxylates depends on the electron-
withdrawing properties of the carboxylic group, as re-
flected by the pKa values. Indeed, as it can be seen in
Fig. 1, the involvement of phenyl groups of the starting
organobismuth compounds both under air and inert
atmosphere decreases according to the pKa value. In
the cases of the stronger acids the effect of oxygen is neg-
ative: the involvement of phenyl groups in the reactions
with 1i (pKa = 0.70) and 1g (pKa = 0.23) is lower under
air than that under argon. In the case of the weaker
acids this effect is positive: the involvement of phenyl
groups increases in the presence of oxygen. The effect
of oxygen is more marked in the cases of acids with
pKa values higher than 4. Among all the organobismuth
compounds studied, the valerate 1d (pKa = 4.82) showed
the highest reactivity both under air and inert atmo-
sphere (298% and 219%, respectively) (Table 4, entry
4). The propionate 1c (pKa = 4.87) and the pivalate 1e
(pKa = 5.03) showed slightly lower reactivity both under
air and argon (Table 4, entries 3 and 5). In the case of 1e,
an increased steric hindrance in the compound can ac-
count for this observation. Although the acetate 1b
(pKa = 4.75) and the propionate 1c have pKa values
close to that of 1d, their lower reactivity is probably
due to the lower solubility of the corresponding organo-
bismuth(III) intermediates. The monochloroacetate 1h
(pKa = 2.85) and the formate 1a (pKa = 3.75) are be-
tween the bismuth(V) derivatives of the stronger acids
and of the weaker acids and the effect of oxygen is posi-
tive for both (Fig. 1). The activity of 1h is higher under
argon than that of the acetate 1b, while the order is re-
versed under air.
2.4. Possible reaction pathways
The general mechanism of the Heck-type palladium
catalyzed C-arylation reaction of alkenes is now well
established [23,24]. The catalytic cycle includes four
Fig. 1. Effect of the pKa value of the acids included in the triphenylbismuth dicarboxylates and the reaction atmosphere on the total involvement of
phenyl groups. The reactions were performed in CH3CN at room temperature for 24 h with the ratio [Bi]:4:PdCl2 (1:3:0.04).

3658
D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
main steps: activation of the catalyst, oxidative addition,
migratory insertion and palladium hydride elimination
[24]. Although the mechanism of the investigated
reaction with triarylbismuth dicarboxylates is not fully
elucidated, we assume that the key process, the
C-phenylation reaction, occurs in a similar way to that
for triarylantimony(V) dicarboxylates studied previ-
ously [1,2].
When Pd(II) salts are used as the catalyst, a transmet-
allation reaction to yield a phenylpalladium intermedi-
ate likely occurs in the first step (Eq. (1)). This
intermediate participates directly in the C-phenylation
reaction with formation of palladium hydride species
(Eq. (2)), which are known to decompose by reductive
elimination to an acid and an active L2Pd(0) species
(Eq. (3)), where L can be phosphine, solvent, olefin or
organobismuth(III) derivative. The L2Pd(0) species are
oxidized by the initial organobismuth(V) compound to
give again the phenylpalladium intermediate (Eq. (4)).
However, it should be noted that Ph3Bi(O2CPh)2 1j does
not react with the palladium complex containing Ph3P
as a ligand (Table 3, entry 7), unlike the triphenylbis-
muth dicarboxylates containing alkyl radical in a car-
boxylic group (Table 1, entry 3 and Table 3, entry 9).
According to the mechanism described above (Eq.
(1)–(4)), one phenyl group of the triphenylbismuth
derivative is involved in the C-phenylation reaction
and the yield of 5a could reach 100%. However, con-
sumption of phenyl groups on side-reactions decreases
this yield. The homo-coupling product, biphenyl 6a,
could be formed by several ways: the palladium-medi-
ated reaction via the Ph2Pd species or self-coupling of
the organobismuth intermediates. The formation of
R2Pd type species in one stage was suggested in the
homo-coupling reaction of R2Te derivatives with palla-
dium(0) [25]. To study the mechanism of the formation
of 6a the coupling reaction of the mixture of triphenyl-
bismuth dipropionate Ph3Bi(O2CEt)2 1c and tris(meta-
tolyl)bismuth dipropionate m-Tol3Bi(O2CEt)2 3a taken
in a 1:1 ratio was carried out under typical conditions
(acetonitrile, r.t., under air, PdCl2 (4 mol%)). Three
products were obtained: biphenyl 6a, 3-methyl-biphenyl
and 3,30-dimethyl-biphenyl 6c, in 35%, 73% and 35%
yield, respectively (Scheme 4). This statistic distribution
of the products (1:2:1), where 3-methyl-biphenyl being
the major one, indicates two important points: no self-
coupling takes place in the system, and diarylpalladium
species are formed via two successive steps (Scheme 5,
route B) (the homo-coupling products 6a and 6c would
otherwise be the major ones (Scheme 5, route A)).
Another evidence for the formation of biaryl occur-
ring via two successive steps is a decrease in the yield
of 6a in the C-phenylation reaction of 4 with 1c under
typical conditions with different 4:1c ratios (Fig. 2).
The yield of 6a is reduced from 136% in the absence
of 4 to 78% in the presence of a 10-fold excess of 4.
Simultaneously, the yield of the C-phenylation product
5a increases from 0% to 79%, respectively. These facts
indicate that the phenylpalladium species PhPdX is
formed during the first stage and reacts either with 4
(Eq. (2)) or with the organobismuth compounds. Other-
wise, the yields of the reaction products would be less
significantly affected. According to the obtained results,
the reaction rate of the PhPdX species with the initial 1c
(Eq. (5)) is higher than that with 4 (Eq. (2)). When 4 and
1c were reacted in a 1:1 ratio, the C-phenylation product
5a and biphenyl 6a were obtained in 43% and 108%
yield, respectively.
Ph3BiX2 þ ðLÞ PdX2 ! ½PhðLÞ PdXꢀ þ Ph2BiX3
ð1Þ
2
2
H
[Ph(L)2PdX]
+
CO2Me
ð2Þ
Ph
+ [H(L)2PdX]
CO2Me
½HðLÞ PdXꢀ ! ðLÞ Pd þ HX
ð3Þ
ð4Þ
2
2
Ph3BiX2 þ ðLÞ Pd ! ½PhðLÞ PdXꢀ þ Ph2BiX
2
2
In the case of triarylantimony(V) derivatives the nat-
ure of the X group has a strong effect on the oxidative
addition process. Palladium insertion along the Ph–Sb
bond of triphenylantimony dicarboxylates occurs with
the participation of a carboxylic group. Conversely, all
halides Ph3SbX2 (X = F, Cl, Br) show a very low or
no reactivity [2]. The triphenylbismuth(V) derivatives
are more reactive due to the lower energy of the Ph–Bi
bond. Ph3BiCl2 has a similar activity to that of the tri-
phenylbismuth dicarboxylates (Tables 2 and 4). Another
difference between antimony and bismuth derivatives is
the effect of phosphines on the transmetallation and
the oxidative addition steps. The presence of strongly
binding ligands such as Ph3P in the coordination sphere
of palladium induces a substantial steric hindrance in
both of these steps in the case of the triphenylantimony
dicarboxylates and the reaction is stopped [2]. Contrast
to that, as it can be seen in Tables 1 and 3, the presence
of phosphine ligands affects the C-phenylation reaction
of 4 with the triphenylbismuth dicarboxylates (Eq.
(2)), decreasing the yield of 5a, and does not affect the
homo-coupling process. This fact indicates that the
transmetallation and the oxidative addition take place
even if the palladium catalyst contains bulky ligands.
PdCl2
m-Tol2
m-Tol-Ph
+
Ph2
Ph3Bi(O2CEt)2 m-Tol Bi(O CEt)
+
+
3
2
2
6a
35%
6c
35%
1c
3a
73%
Scheme 4.

D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
3659
A
Ar2Pd
- ArBiX2
ArPdX
Ar3BiX2
Ar2Pd
+Pd(0)
B
Ar2
ArPdX
- Pd(0)
- Ar2BiX
[Bi(III,V)]
Ar
Ar2Pd
Scheme 5.
140
120
100
80
5a (air)
5a (argon)
6a (air)
6a (argon)
7a (air)
7a (argon)
60
40
20
0
0
2
4
6
8
10
4:1c (molar ratio)
Fig. 2. Effect of the molar ratio 4:1c on the yields of the reaction products (CH3CN, r.t., 24 h, with 4 mol% of PdCl2).
The same reactions were carried out under argon as
well. As shown in Fig. 2, the yields of 5a and 6a were
reduced. Of note, when an excess of 4 is used the total
involvement of phenyl groups decreases both under air
and under argon. In the former case this effect is neg-
ligible, from 275% in the absence of 4 to 255% in the
presence of a 10-fold excess of it. Under argon, how-
ever, this effect is more pronounced, from 267% to
179%, respectively. This indicates that an oxygen-sensi-
tive organobismuth intermediate is formed in the pres-
ence of a large excess of 4. Analogously to the
organoantimony derivatives it can be assumed that
this intermediate may be the Ph2BiX derivative formed
according to Eq. (4). In the presence of a large excess
of 4 the rate of the C-phenylation reaction (Eq. (2)) in-
creases compared to that with the organobismuth
compound (Eq. (5)) and the Ph2BiX species accumu-
lates in the reaction mixture. In the presence of oxygen
Ph2BiX is oxidized in the coordination sphere of palla-
dium to a bismuth(V) derivative, which can oxidize
Pd(0) to the PhPdX species. This process likely occurs
via mechanism similar to that observed for the corre-
sponding organoantimony derivative Ph2SbX [1] (Eq.
(6)). Indeed, when Ph2BiCl and 4 (1:3) were reacted
in CH3CN at room temperature under argon in the
presence of PdCl2 (4 mol%), only trace amount of
the products were found (the total involvement of
the phenyl groups 6%). However, the same reaction
carrying out in the presence of oxygen affords methyl
cinnamate 5a, biphenyl 6a and benzene in the yield
of 11%, 10% and 10%, respectively. When methyl
acrylate 4 is absent or taken in a stoichiometric ratio
(1:1) to Ph3BiX2, the reaction of PhPdX with the start-
ing Ph3BiX2 (Eq. (5)) becomes the main pathway.
According to this reaction the homo-coupling product
6a can be obtained in 50% yield. The Ph2BiX3 species
formed in this reaction are unstable and probably
more reactive than the starting Ph3BiX2. No data sup-
porting the existence of such organobismuth(V) deriv-
atives could however be found in the literature.
Ph2BiX3 species are able to oxidize the Pd(0) species
into PhPdX (Eq. (7)), which reacts with 4 (Eq. (2))
or with the organobismuth(III) derivatives (Eqs. (8)
and (9)), increasing the yield of the products.

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D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
derivatives containing the weaker acids, and the acids
formed according to Eq. (3) are strong enough to
provide the dephenylation of the bismuth(III) com-
pound. The low activity of the derivatives containing
stronger acids, 1g and 1i, and the corresponding very
low yield of 7a seem to suggest a different mechanism
governs their participation in the palladium mediated
processes.
PhPdX þ Ph3BiX2 ! Ph2 þ Ph2BiX3 þ Pdð0Þ
ð5Þ
0
½Pdꢀ
2Ph2BiX þ O2 ! 2Ph2BiðOÞX P!d PhPdX þ PhBiO ð6Þ
Ph2BiX3 þ Pdð0Þ ! PhPdX þ PhBiX2
PhPdX þ Ph2BiX ! Ph2 þ PhBiX2 þ Pdð0Þ
PhPdX þ PhBiX2 ! Ph2 þ BiX3 þ Pdð0Þ
ð7Þ
ð8Þ
ð9Þ
However, the mechanism suggested above can ex-
plain the involvement of only two phenyl groups of
the starting 1c in the absence of oxygen. As it can be
seen from the obtained results (Fig. 2) the total involve-
ment of phenyl groups is more than 200% under argon
when the 4:1c molar ratio is 1:1 (243%) or when methyl
acrylate is absent (267%). These results are similar to
those of the corresponding reactions under air (267%
and 275%, respectively). This can be explained by the
participation of the Ph2BiX3 species formed according
to Eq. (5), which should be a stronger oxidant than
Ph3BiX2. Ph2BiX3 is able to oxidize the PhPdX interme-
diate to the palladium(IV) species Ph2PdX2 (Eq. (10)),
which decomposes into 6a and the palladium(II) salt
PdX2 (Eq. (11)). Thus, palladium(II) remains in the
reaction mixture and can be involved in the transmetal-
lation reaction with organobismuth derivatives. As a
consequence, oxygen must not affect significantly the
palladium-mediated process in the absence of olefin,
which is what is being observed experimentally.
Ph2BiX þ HX ! PhBiX2 þ PhH
ð12Þ
Attempts to prove the mechanistic points discussed
above by 1H NMR spectroscopy were made in the
C-arylation reaction of 4 with tris(para-tolyl)bismuth
dipivalate p-Tol3Bi(O2CBu-t)2 2a. This system was se-
lected for the following reasons. The initial compounds
as well as the organic products had clear and easily
identifiable NMR signals. Moreover, we assume that
the presence of the pivalic group will increase the solu-
bility of the proposed organobismuth intermediates.
D3CCN was used as a solvent. The reaction was car-
ried out under air at room temperature. After 1 h,
the resonances of the starting 2a disappeared com-
pletely [7.93 (d, ortho-protons), 7.43 (d, meta-protons),
2.37 (s, CH3) and 0.97 (s, Bu-t) ppm]. At the same time
1
a white solid precipitated in the NMR tube and the H
spectra showed a quite complicated pattern. Except for
the strong resonances [doublets at 7.51 and 7.25 ppm]
of tolyl groups of the C-arylation and biaryl products,
upfield-shifted of those of the starting 2a, only strong
resonances of the tolyl group of a new species [doublets
at 8.34 and 7.69 ppm], downfield-shifted significantly of
those of the starting 2a, were detected in the spectra.
These resonances can be associated with the organobis-
muth(V) derivative p-Tol2Bi(O2CBu-t)3, the p-Tol–Bi
bond of which is more polar than that of 2a due to
the effect of three carboxylic groups. One more doublet
due to ortho-protons of the tolyl group at 7.60 ppm,
upfield-shifted of those of the starting 2a, was observed
in the spectra, and may correspond to an organobis-
muth(III) derivative. However, precipitation of a solid
in the NMR tube did not allow for a quantitative
determination of all species present in the reaction
mixture.
The proposed bismuth intermediates such as Ar2-
BiX3, Ar2BiX or ArBiX2 are relatively unstable. They
are able to react with other molecules of the organo-
bismuth compounds in a ligand exchange type reac-
tion or form insoluble oxo-complexes, which are
probably inactive in the palladium-catalyzed reactions.
These side-reactions affect the understanding of the
whole mechanism of the participation of the triarylbis-
muth dicarboxylates in the palladium-mediated reac-
tions described above. Further studies are now
underway to better understand the various intertwined
mechanistic facets of the catalytic reaction reported in
this work.
PhPdX þ Ph2BiX3 ! Ph2PdX2 þ PhBiX2
Ph2PdX2 ! Ph2 þ PdX2
ð10Þ
ð11Þ
Arylbismuth(III) derivatives can interact with acids
to give benzene [26]. This reaction occurs easily with
strong acids and requires heating in the cases of weak
carboxylic acids. Triarylbismuth Ar3Bi in the reaction
with an acid, generally, converts into an ArBiX2 spe-
cies. To achieve full dearylation of Ar3Bi the presence
of a large excess of the acid is necessary [26c–e]. We
suggest that the acid generated in the reductive elimi-
nation stage (Eq. (3)) can react with the organobis-
muth(III) intermediates Ph2BiX to give 7a (Eq. (12)).
An increase in the yield of 7a in almost all reactions
carried out under argon confirms this suggestion be-
cause the bismuth(III) compounds are accumulated
in the reaction mixture. It is interesting to note that
the yield of 7a under air is the highest in the cases
of the bismuth(V) compounds containing the carbox-
ylic acids with middle pKa values (formate 1a (62%)
and monochloroacetate 1h (33%)) (Table 4, entries 1
and 9). The organobismuth compounds containing
other carboxylic acids, either stronger or weaker than
the two above mentioned, provide significantly lower
yields of 7a. This indicates that the triphenylbismuth
dicarboxylates containing these acids have transition
properties in between those of the derivatives contain-
ing weaker or stronger acids. They are active like the

D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
3661
3. Conclusion
with an alkali solution until the yellow color disap-
peared, then dried with Na2SO4 and distilled. All sol-
vents were distilled prior to use. Pd(OAc)2 [28],
Pd2(dba)3 [29], Pd(Ph3P)2Cl2 [30] were prepared by the
reported methods, and PdCl2, dppm, dppe, dppp, dppb,
BINAP, xantphos were commercially available. Ph2BiCl
was prepared by a treatment of Ph3Bi and BiCl3 in a 2:1
ratio in dry ether [31].
Readily available triarylbismuth(V) dicarboxylates
Ar3Bi(O2CR)2 are very reactive reagents for the palla-
dium-mediated formation of new C–C bonds. The
Heck-type C-arylation reaction can be easily performed
at room temperature in CH3CN as the best solvent, with
PdCl2 (4 mol%) as the most effective catalyst. The
homo-coupling process competes with the C-arylation
reaction due to the low energy of the C–Bi bond. The
nature of the carboxylic group affects the activity of
the organobismuth derivatives and the competition be-
tween the C-arylation reaction and the homo-coupling
process. When derivatives containing weak carboxylic
acids were used in the reaction the highest reactivity of
the triarylbismuth dicarboxylates was observed, with al-
most all three aryl groups involved in the reactions. Tri-
arylbismuth divalerate Ar3Bi(O2CBu-n)2 is the most
effective in the C-arylation reaction. The derivatives con-
taining strong acids showed the highest selectivity. The
C-arylation reaction is significantly inhibited by the
presence of strongly binding ligands on the palladium,
such as phosphines. The reaction atmosphere also affects
the reactions. The reactivity of triarylbismuth dicarb-
oxylates and the selectivity of the C-arylation reaction
decrease when the reactions are performed under argon.
Triarylbismuth(V) dicarboxylates Ar3Bi(O2CR)2 are
significantly more reactive than triarylantimony(V)
dicarboxylates studied previously. However, the selec-
tivity of the C-arylation is significantly higher in the case
of the antimony derivatives. Unlike triphenylantimony
dichloride, Ph3BiCl2 is active in the C-phenylation reac-
tion. In the case of organoantimony(V) compounds the
nature of the carboxylic group has a little effect on the
reaction whereas it is important in the reactions with
the organobismuth(V) derivatives. Oxygen and phos-
phine ligands affect the C-arylation reaction both with
bismuth and with antimony derivatives.
4.2. Preparation of Ph3Bi(O2CH)2 1a using t-BuOOH
t-BuOOH (5 mmol) was added dropwise to a stirred
cold (5–10 °C) solution of Ph3Bi (5 mmol) and HCOOH
(10 mmol) in Et2O (50 ml). The reaction mixture was
kept in the dark for 24 h at room temperature. The sol-
vent was distilled off under reduced pressure and the so-
lid residue was purified by recrystallization (CHCl3/
hexane) to afford 1a (2.1 g, 80%), m.p. 150–152 °C (de-
comp.) (lit. [32] 140–150 °C (decomp.)).
Other organobismuth compounds were prepared by
the same procedure:
Triphenylbismuth diacetate 1b: m.p. 187–189 °C (lit.
[32] 187–189 °C).
Triphenylbismuth dipropionate 1c: m.p. 156 °C (lit.
[32] 157–159 °C).
Triphenylbismuth divalerate 1d: m.p. 89 °C (lit. [32]
91 °C).
Triphenylbismuth dipivalate 1e: m.p. 142 °C (lit. [32]
146–148 °C).
1
Triphenylbismuth dihexanoate 1f: m.p. 73–76 °C; H
NMR: d 8.16 (d, J = 7.3 Hz, 6H), 7.61–7.42 (m, 9H),
2.05 (t, J = 7.3 Hz, 4H), 1.45–1.30 (m, 4H), 1.18–0.86
(m, 8H), 0.73 (t, J = 7.3 Hz, 6H). Anal. Calc. for
C30H37O4Bi: C, 53.7; H, 5.6. Found: C, 53.5; H, 5.6%.
Triphenylbismuth bis(trifluoroacetate) 1g: m.p. 143–
144 °C (lit. [32] 143–144 °C).
Triphenylbismuth bis(monochloroacetate) 1h: m.p.
110 °C (lit. [32] 155–156 °C); 1H NMR: d 8.18 (d;
J = 7.3 Hz, 6H), 7.67 (t; J = 7.3 Hz, 6H), 7.54 (t;
J = 7.3 Hz, 3H), 3.86 (s; 4H). Anal. Calc. for
C22H19Cl2O4Bi: C, 42.1; H, 3.1. Found: C, 42.0; H,
3.1%.
4. Experimental
4.1. General methods
Triphenylbismuth bis(trichloroacetate) 1i: m.p.
158 °C (lit. [32] 158 °C).
Gas chromatographic analyses were performed with
a LKhM-80 chromatograph using helium as the carrier
gas, column 300 cm length, 15%-DNF on the Chrom-
aton N-AW-DMCS at 80 °C (for analyze of benzene)
and column 240 cm length, 15%-Apiezon-L on the
Chromaton N-AW-DMCS at 130 °C (for analyze of
chlorobenzene) and 220 °C (for analyze of methyl cinna-
mate and biphenyl). 1H NMR spectra were measured on
a Bruker Avance DPX-200 spectrometer for solutions in
CDCl3, D3CCN.
Triphenylbismuth dibenzoate 1j: m.p. 166–168 °C (lit.
[32] 167–169 °C).
Tris(para-tolyl)bismuth dipivalate 2a: m.p. 167–
1
171 °C; H NMR: d 8.00 (d, J = 8.3 Hz, 6H), 7.34 (d,
J = 8.3 Hz, 6H), 2.37 (s, 9H), 0.96 (s, 18H). Anal. Calc.
for C31H39O4Bi: C, 54.4; H, 5.7. Found: C, 54.4; H,
5.6%.
Tris(meta-tolyl)bismuth dipropionate 3a: m.p. 90 °C;
1H NMR: d 7.95 (d, J = 8.3 Hz, 6H), 7.49 (t, J = 7.7 Hz,
3H), 7.28 (d, J = 7.3 Hz, 3H), 2.41 (s, 9H), 2.17–2.05 (m,
4H), 0.94 (t, J = 7.7 Hz, 6H). Anal. Calc. for C27H31-
O4Bi: C, 51.6; H, 4.9. Found: C, 51.4; H, 4.9%.
t-BuOOH was prepared by the method of Milas and
Surgenor [27]. Commercial methyl acrylate was washed

3662
D.V. Moiseev et al. / Journal of Organometallic Chemistry 690 (2005) 3652–3663
Triphenylbismuth dichloride: m.p. 149–150 °C (lit.
[32] 146–147 °C).
Acknowledgment
We thank Dr. Paolo Marcazzan (University of
British Columbia, Vancouver, Canada) for fruitful
discussions.
4.3. Typical procedure for the C-phenylation reaction
A mixture of Ph3Bi(O2CH)2 (0.265 g, 0.5 mmol),
PdCl2 (3.6 mg, 0.02 mmol), methyl acrylate (0.135 ml,
1.5 mmol) in acetonitrile (6 ml) was placed in a 50 ml
tube. The tube was sealed and the reaction mixture
was kept at 50 °C for 3 h. The solvent was then evapo-
rated under reduced pressure and analyzed by GLC.
The solid residue was purified from inorganic products
by elution through a short column on silica gel using a
mixture of hexane–ethyl acetate (v/v 4:1) as the eluent.
The filtrate was analyzed by GLC. Methyl cinnamate
(0.057 g), biphenyl (0.035 g) and benzene (0.023 g) were
found.
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1
4.6. Procedure for H NMR spectroscopic study
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A
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1
monitored by H NMR within one day.

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