Effect of π-accepting substituent on the reactivity and spectroscopic characteristics of triarylbismuthanes and triarylbismuth dihalides

Article abstract of DOI:10.1016/j.jorganchem.2004.07.055

Competitive chlorination of p-substituted triarylbismuthanes 1 [(p-XC₆H₄)₃ Bi; a: X = OMe, c: Cl, d: CO₂Et, e: CF₃, f: CN, g: NO₂] and trimesitylbismuthane (2,4,6-Me₃C₆H₂) ₃Bi 1h by sulfuryl chloride was carried out against 1b (X = H) and the effect of these substituents on the formation of triarylbismuth dichlorides 2 was studied. The relative ratios 2/2b decreased with increasing electron-withdrawing ability of the substituents (2a/2b = 53/47, 2c/2b = 33/67, 2d/2b = 35/65, 2e/2b = 29/71, 2f/2b = 16/84, 2g/2b = 0/100, 2h/2b = 46/54), indicating a lowering of reactivity of the lone pair on the bismuth atom. Pd-Catalyzed degradation of 2a-g and their difluorides 3 giving biaryls 4 was promoted by the electron-withdrawing p-substituents in the equatorial aryl groups but suppressed by the more electronegative fluorine atoms in the apical positions. This is in fairly good accord with the stability of the trigonal bipyramidal geometry. The 13 study of 1-3 showed that the signals due to the ipso carbons (C1) attached to the bismuth atom shift downfield with increasing electron-withdrawing nature of the p-substituents. No such tendency was observed in other aromatic ring carbons. The electronic effect on the C1 atoms, similar to that on the chlorination of 1 and degradation of 2 and 3, indicates the significant participation of the C1 atoms in these reactions through the Bi-C1 bonds.

Full text of DOI:10.1016/j.jorganchem.2004.07.055

Journal of Organometallic Chemistry 689 (2004) 3395–3401
www.elsevier.com/locate/jorganchem
Effect of p-accepting substituent on the reactivity and
spectroscopic characteristics of triarylbismuthanes
and triarylbismuth dihalides
*
A.F.M. Mustafizur Rahman, Toshihiro Murafuji , Motoko Ishibashi,
**
Youhei Miyoshi, Yoshikazu Sugihara
Department of Chemistry, Faculty of Science, Yamaguchi University, Yamaguchi 753-8512, Japan
Received 27 May 2004; accepted 29 July 2004
Available online 11 September 2004
Abstract
Competitive chlorination of p-substituted triarylbismuthanes 1 [(p-XC6H4)3Bi; a: X = OMe, c: Cl, d: CO2Et, e: CF3, f: CN, g:
NO2] and trimesitylbismuthane (2,4,6-Me3C6H2)3Bi 1h by sulfuryl chloride was carried out against 1b (X = H) and the effect of these
substituents on the formation of triarylbismuth dichlorides 2 was studied. The relative ratios 2/2b decreased with increasing electron-
withdrawing ability of the substituents (2a/2b = 53/47, 2c/2b = 33/67, 2d/2b = 35/65, 2e/2b = 29/71, 2f/2b = 16/84, 2g/2b = 0/100, 2h/
2b = 46/54), indicating a lowering of reactivity of the lone pair on the bismuth atom. Pd-Catalyzed degradation of 2a–g and their
difluorides 3 giving biaryls 4 was promoted by the electron-withdrawing p-substituents in the equatorial aryl groups but suppressed
by the more electronegative fluorine atoms in the apical positions. This is in fairly good accord with the stability of the trigonal
bipyramidal geometry. The 13C NMR study of 1–3 showed that the signals due to the ipso carbons (C1) attached to the bismuth
atom shift downfield with increasing electron-withdrawing nature of the p-substituents. No such tendency was observed in other
aromatic ring carbons. The electronic effect on the C1 atoms, similar to that on the chlorination of 1 and degradation of 2 and
3, indicates the significant participation of the C1 atoms in these reactions through the Bi–C1 bonds.
Ó 2004 Elsevier B.V. All rights reserved.
Keywords: Bismuth; Electron-withdrawing group; Oxidative chlorination; Biaryl formation; ipso-Carbon; 13C NMR study
1. Introduction
and carbonyl compounds [2]. Despite such availability,
however, the number of this class of derivatives is not
so large since the aryl groups introducible into the bis-
muth center have been limited. In particular, few reports
on the derivatives bearing p-accepting substituents have
appeared in the literature [3] due to lack of general syn-
thetic methods for the parent triarylbismuthanes. It is an
important issue for us to know how electronic effect af-
fects the reactivity and properties of organobismuth
compounds. In order to address this issue, we have re-
cently established a convenient method for the synthesis
of triarylbismuthanes 1d, 1f and 1g bearing a p-accept-
ing ester, cyano and nitro group in the p-position of each
aromatic ring, respectively [4], the synthesis of which has
Organobismuth compounds have been receiving
increasing interest owing to their versatile reactivity
and properties [1]. Triarylbismuth dihalides (Ar3BiX2;
X = F, Cl) are utilized as stable and useful precursors
of various organobismuth(V) derivatives. From the
viewpoint of organic transformation, triarylbismuth
dichlorides are efficient arylating reagents of phenols
*
Corresponding author. Fax: +81 83 933 5738.
Fax: +81 83 933 5730.
**
E-mail addresses: murafuji@yamaguchi-u.ac.jp (T. Murafuji),
sugihara@yamaguchi-u.ac.jp (Y. Sugihara).
0022-328X/$ - see front matter Ó 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.07.055

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A.F.M. Mustafizur Rahman et al. / Journal of Organometallic Chemistry 689 (2004) 3395–3401
been difficult by conventional methods. This paper de-
scribes the electronic effect of p-substituents on the oxi-
sulfur atom [9]. The competitive chlorination of triphe-
nylstibine 1i (2i/2b = 62/38) reflects the lower s-character
of the lone pair on the antimony atom.
dative chlorination of
1 to form triarylbismuth
dichlorides 2, Pd-catalyzed biaryl formation of 2 and
difluorides 3 and spectroscopic characteristics of 1–3.
Systematic studies from the viewpoint of the electronic
effect have been restricted in organobismuth chemistry
[3b,5], although the structural aspects from the steric
viewpoint based on kinetic stabilization have so far been
discussed extensively [6].
2.2. Synthesis of triarylbismuth difluorides 3 and their
characterization by 19F NMR spectrum
Recently, it has been found that triarylbismuth diflu-
orides are versatile precursor for the synthesis of bis-
muthonium salts [10–12]. Development of these
methods enables exploration of new research fields of
organobismuth(V) derivatives which have been inacces-
sible by conventional methods. The number of difluo-
rides has been, however, extremely limited compared
to triarylbismuthanes and triarylbismuth dichlorides.
Thus, a series of difluorides 3a–g were synthesized from
dichlorides 2a–g by the chlorine–fluorine exchange with
use of AgF (Scheme 1) and studied by 19F NMR spec-
trum. Few derivatives have been characterized by 19F
NMR spectrum [13]. The exchange reaction proceeded
smoothly irrespective of the nature of the p-substituents.
The signals due to the fluorine atoms of 3 appeared
around dF ꢀ160.0 as a sharp singlet and their chemical
shifts did not show the dependence of the p-substituents
(Table 1). The similarity of the dF values in 3 indicates
that the geometry of the bismuth center in triarylbis-
muth dihalides is not affected by the electronic effect
of the p-substituents and governed by the apicophilicity
of the halogen atoms, thus adopting a trigonal bipyram-
idal structure like 2b [14b] and 3b [14a]. Recently, sev-
eral examples of reversed apicophilicity have been
found in the trigonal bipyramidal phosphorus systems
[15]. Such structural characteristics of triarylbismuth
dihalides is in contrast to those of the related organobis-
muth(V) derivative pentaarylbismuth [5c,16], in which
the geometry of the bismuth center changes from the
square pyramidal to the trigonal bipyramidal depending
on the electronic effect of the aryl groups.
2. Results and discussion
2.1. Oxidative chlorination of triarylbismuthanes 1 with
sulfuryl chloride
While the chlorination of 1a–e and 1h completed
quickly, that of 1f and 1g required a longer reaction time
(1–2 h) for completion (Scheme 1). Competitive chlorin-
ation of 1 carried out against 1b revealed that the relative
ratios 2/2b (estimated by 1H NMR) decrease with
increasing electron-withdrawing nature of the p-substitu-
ent (Scheme 2). In the competitive chlorination of 1g, 2g
did not form at all. As shown in Fig. 1, a good linear rela-
tionship with a negative slope was obtained between
these ratios and the Hammett rp constants [7] (n = 6,
r = 0.90). The bulky mesityl groups minimally affected
the chlorination of 1h (2h/2b = 46/54). Such electronic ef-
fect should be stressed since the lone pair of the bismuth
atom is inherently an s-character and cannot efficiently
overlap with the 2p orbitals of the aromatic ring carbons,
although the lone pair on the phosphorus atom of tria-
rylphosphines is delocalized into the aromatic rings by
the electron-accepting p-substituents [8]. The lowered
reactivity of 1 by the electron-accepting p-substituents
is consistent with the generation of chloronium cation,
which is proposed in the chlorination of sulfides at the
Scheme 1.

A.F.M. Mustafizur Rahman et al. / Journal of Organometallic Chemistry 689 (2004) 3395–3401
3397
Scheme 2.
Table 1
19F NMR spectral data (d) and coupling constants (JCF) of 3 in CDCl3
2
3
dF
dC, JCF
dC, JCF
a
a
3a
ꢀ158.45 (s)
–
153.55 (t, 9.2)
–
134.31 (t, 3.1)
3bb ꢀ161.26 (s)
3c
3d
3e
3f
ꢀ160.08 (s)
ꢀ160.37 (s)
150.83 (t, 10.0) 135.24 (t, 3.1)
157.65 (t, 9.2)
134.13 (t, 3.8)
134.76 (t, 3.8)
ꢀ161.92 (s), ꢀ64.44 (s, CF3) 156.22 (t, 8.4)
ꢀ162.16 (s)
157.12 (t, 10.0) 134.98 (t, 3.8)
158.41 (t, 10.0) 135.29 (t, 3.8)
3g
ꢀ158.68 (s)
Not observed.
a
b
In [13a], the dF value of 3b is reported to be ꢀ161.3.
in 85–90% yields (Eq. 1). The similar reaction using
Pd(PPh3)4 catalyst, however, proceeded sluggishly,
depending on the p-substituents. In order to compare
the effect of the substituents, the coupling reaction was
carried out independently for 2a, 2b, 2e, 2f and their
difluorides 3 in CDCl3 at 40 °C for 1 h and the recovery
(%) of the respective dihalides was estimated by 1H
NMR spectrum. The results are as follows: 2a (96), 2b
(82), 2e (39), 2f (27), 3a (96), 3b (82), 3e (74) and 3f
(67%). With increasing electron-withdrawing nature of
the substituents, the reactivity increased and such ten-
dency was more remarkable in 2. These findings are
fairly in good accord with the stability of the trigonal
bipyramidal structure based on the apicophilicity [18].
Fig. 1. Hammett plot.
ð1Þ
2.3. Biaryl formation by Pd-catalyzed coupling reaction of
2 and 3
2.4. Characterization of 1–3 by 13C NMR spectrum
It is known that 2b undergoes Pd-catalyzed degrada-
tion to form 4b quantitatively [17]. All the three phenyl
groups are coupled as the product. In the presence of
Pd(OAc)2 catalyst, the coupling reaction of p-substi-
tuted 2 produced the corresponding biaryls 4 quickly
The aromatic ring carbons of 1–3 were all assigned
and their chemical shifts (dC) are summarized in Table
2, along with those of the parent mono-substituted ben-
zenes 5 [19]. The signals due to the ipso-carbons (C1) at-
tached to the bismuth atom appeared largely downfield

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A.F.M. Mustafizur Rahman et al. / Journal of Organometallic Chemistry 689 (2004) 3395–3401
Table 2
13C NMR spectral data (d) of 1–3 in CDCl3
C1
C2
C3
C4
C5
CH2
CH3
a
b
c
145.06
155.09
152.70
161.66
159.85
162.20
164.40
138.71
137.53
138.53
137.42
137.75
137.95
138.34
116.27
130.47
130.67
131.03
127.32
133.95
125.48
159.26
127.73
134.13
130.18
130.51
111.42
148.24
55.01
1
d
ea
f
166.62
124.11
118.52
61.43
14.60
g
a
b
c
146.73
155.63
153.18
159.82
158.31
159.16
160.32
135.90
134.17
135.55
134.25
134.87
135.05
135.41
116.72
131.43
131.66
132.54
128.65
135.05
126.41
161.72
131.19
138.49
133.58
134.04
116.27
149.94
55.60
14.23
2
d
ea
f
165.21
123.15
116.99
61.69
g
a
b
c
144.36
153.55
150.83
157.65
156.22
157.12
158.41
135.38
134.31
135.24
134.13
134.76
134.98
135.29
116.55
131.85
131.45
132.15
128.26
134.74
126.02
162.15
131.43
138.84
133.96
134.47
116.68
150.50
55.49
14.24
3
d
ea
f
165.35
123.15
117.02
61.65
g
a
b
c
d
e
f
120.7
128.5
126.5
132.4
131.8
132.8
134.7
129.5
128.5
129.5
128.0
128.8
129.2
129.8
114.1
128.5
128.7
129.5
125.3
132.1
124.2
159.9
128.5
134.9
131.0
131.0
112.8
149.1
5b
g
a
Quartet, JCF=around 3.6, 33.0 and 271.3 Hz for C3, C4 and C5, respectively.
5a–d, 5f and 5g: [19a]. 5e: [19b].
b
compared to those of the parent 5 (about 25–30, 27 and
25 ppm in 1, 2 and 3, respectively). A similar tendency
was found with respect to the C2 atoms, but the differ-
ences were not so large as observed in the C1 atoms
(about 9 ppm in 1 and about 6 ppm in 2 and 3). The cou-
pling constants JCF and JCF in 3 were around 9.5 and
3.5 Hz, respectively, and did not show the clear depend-
ence of the p-substituent (Table 1). The chemical shifts
of the C3 and C4 atoms were close to those of the cor-
responding carbon atoms of 5. With respect to the C4
atoms, in particular, little difference was observed be-
tween 1 and 5. These findings suggest that the effect of
the bismuth atom is inductively transmitted to the aro-
matic ring carbons.
An outstanding feature is in the chemical shifts of the
ipso C1 atoms, which shifted downfield with increasing
electron-withdrawing nature of the p-substituents. No
such tendency was observed in other aromatic carbons.
It is established that the chemical shifts of the C1 atom
of 5 are correlated with the Hammett rp constants and
total charge density on the carbon atom [20]. Linear
relationships were shown between the rp constants
(n = 7) and the C1 chemical shifts of 1–3 as well as those
of 5 with the following positive slopes (1: 17.0, r = 0.89,
2: 11.7, r = 0.8l, 3: 12.1, r = 0.83, 5: 12.0, r = 0.88). The
electronic effect on the C1 atoms, which is similar to that
on the chlorination of 1 and degradation of 2 and 3,
indicates the significant participation of the C1 atoms
in these reactions through the Bi–C1 bonds.
A series of pentacoordinate trifluorosilicates bearing
various p-substituents in the aromatic ring have been
characterized by 13C NMR spectrum in comparison
with the parent tetracoordinate silanes [21]. This study
suggests that p-polarization takes place in the aromatic
rings of the silicates with change in the geometry from
the tetracoordinate to the pentacoordinate silicon cen-
ter. Table 3 shows the differences in chemical shift be-
tween 1 and 2 (D2 = d2 ꢀ d1) and between 1 and 3
(D3 = d3 ꢀ d1) when the geometry of the bismuth center
changes from the pyramid of 1 to the trigonal bipyramid
2
3

A.F.M. Mustafizur Rahman et al. / Journal of Organometallic Chemistry 689 (2004) 3395–3401
3399
Table 3
The difference in the chemical shifts between 1 and 2 (D2) and between 1 and 3 (D3)s
D2
D3
C1
C2
C3
C4
C1
C2
C3
C4
a
b
c
d
e
f
1.67
ꢀ2.81
ꢀ3.36
ꢀ2.98
ꢀ3.17
ꢀ2.88
ꢀ2.90
ꢀ2.93
0.45
0.96
0.99
1.51
1.33
1.10
0.93
2.46
3.46
4.36
3.40
3.53
4.85
1.70
ꢀ0.70
ꢀ1.54
ꢀ1.87
ꢀ4.01
ꢀ3.63
ꢀ5.08
ꢀ5.99
ꢀ3.33
ꢀ3.22
ꢀ3.29
ꢀ3.29
ꢀ2.99
ꢀ2.97
ꢀ3.05
0.28
1.38
0.78
1.12
0.94
0.79
0.54
2.89
3.70
4.71
3.78
3.96
5.26
2.26
0.54
0.48
ꢀ1.84
ꢀ1.54
ꢀ3.04
ꢀ4.08
g
of 2 and 3. The values D2(C1) and D3(C1) increased neg-
atively with increasing electron-withdrawing nature of
the p-substituents and the latter was negatively larger
than the former. The D2(C2) and D3(C2) values were
approximately constant (around ꢀ3 ppm) irrespective
of the p-substituents and apical halogen atoms. With re-
spect to the C3 and C4 atoms, the D values were all pos-
itive and outstanding regularity was not found. These
data show that similar p-polarization arises in the aro-
matic rings of 2 and 3 with the charge distribution of
the C1 and C2 atoms negative and that of the C3 and
C4 atoms positive. Furthermore, the influence of the
p-substituents on the p-polarization is marked in the
C1 carbons with increasing electron-accepting nature
of the substituents and such tendency is more pro-
nounced in 3 rather than 2, although the C2, C3 and
C4 carbons do not suffer from the outstanding substitu-
ent effect in the p-polarization.
(s, 9H), 7.12 (d, 6H, J = 9.1 Hz), 8.42 (d, 6H, J = 9.1
Hz); Anal. Calc. for C21H21BiO3Cl2: C, 41.97; H, 3.45.
Found: C, 41.89; H, 3.52%.
Triphenylbismuth dichloride (2b): Yield 90%; m.p.
1
152–154 °C (lit. [22], 156–158 °C; H NMR d 7.54 (t,
3H, J = 7.3 Hz), 7.67 (t, 6H, J = 7.5 Hz), 8.53 (d, 6H,
J = 8.2 Hz).
Tris(4-chlorophenyl)bismuth dichloride (2c): Yield
1
91%; m.p. 188–190 °C (lit. [23], 170 °C); H NMR d
7.63 (d, 6H, J = 8.7 Hz), 8.47 (d, 6H, J = 8.7 Hz). Anal.
Calc. for C18H12BiCl5: C, 34.82; H, 1.96. Found: C,
35.13; H, 1.97%.
Tris(4-ethoxycarbonylphenyl)bismuth dichloride (2d):
1
Yield 90%; m.p. 142–144 °C (lit. [3c], 138–139 °C); H
NMR d 1.40 (t, 9H, J = 7.1 Hz), 4.41 (q, 6H, J = 7.1
Hz), 8.32 (d, 6H, J = 8.6 Hz), 8.61 (d, 6H, J = 8.6 Hz);
IR (cmꢀ1): 1723, 1584, 1390, 1271, 1104, 1001, 749. Anal.
Calc. for C27H27BiCl2O6: C, 44.71; H, 3.65. Found: C,
44.53; H, 3.74%.
Tris(4-trifluoromethylphenyl)bismuth dichloride (2e):
1
Yield 87%; m.p. 137–138 °C) (lit. [5b], 140–143 °C); H
3. Experimental
NMR d 7.94 (d, 6H, J = 8.4 Hz), 8.71 (d, 6H, J = 8.4
Hz). Anal. Calc. for C21H12BiF9Cl2: C, 35.44; H, 1.67.
Found: C, 35.23; H, 1.69%.
Tris(4-cyanophenyl)bismuth dichloride (2f): Yield
91%; m.p. 189–191 °C; 1H NMR d 7.97 (d, 6H,
J = 8.6 Hz), 8.72 (d, 6H, J = 8.6 Hz); IR (cmꢀ1): 2238,
1575, 1475, 1388, 992, 825. Anal. Calc. for
C21H12BiCl2N3: C, 43.03; H, 2.06; N, 7.17. Found: C,
43.40; H, 2.26; N, 7.40%.
Dichloromethane, acetonitrile and THF were dis-
tilled from calcium hydride under nitrogen before use.
1H and 13C NMR spectra were recorded in CDCl3 on
a BRUKER AVANCE 400S spectrometer with TMS
as an internal standard. 19F NMR spectra were meas-
ured in CDCl3 on a BRUKER AVANCE 400S spec-
trometer with benzotrifluoride (ꢀ64.0 ppm) as an
internal standard. IR spectra were observed as KBr pel-
lets on a Nicolet Impact 410 spectrophotometer.
Tris(4-nitrophenyl)bismuth dichloride (2g): Yield
1
88%; m.p. 175–177 °C (lit. [3b], 165 °C); H NMR d
3.1. Reaction of 1 with sulfuryl chloride: general proce-
dure
8.53 (d, 6H, J = 9.1 Hz), 8.81 (d, 6H, J = 9.1 Hz); IR
(cmꢀ1): 1601, 1559, 1524, 1466, 1389, 1350, 1312,
992, 846, 734. Anal. Calc. for C18H12BiCl2N3O6: C,
33.46; H, 1.87; N, 6.50. Found: C, 33.20; H, 2.06; N,
6.24%.
To a solution of triarylbismuthane 1 (1 mmol) in
dichloromethane (5 ml) was added at room temperature
a 1.0 M solution of sulfuryl chloride in the same solvent
(1 ml). After completion of the reaction (checked by
TLC), the resulting mixture was concentrated to leave
a residue, which was crystallized by an addition of hex-
ane to give the product as colorless crystals.
Tris(2,4,6-trimethylphenyl)bismuth dichloride (2h):
Yield 90%; m.p. 155–160 °C (decomp.) (lit. [23], 150
1
°C, decomp.); H NMR d 2.32 (s, 9H), 2.72 (s, 18H),
7.15 (s, 6H); 13C NMR d 21.24, 25.80, 132.59, 141.57,
142.29, 167.97.
Triphenylantimony dichloride (2i): Yield 92%; m.p.
Tris(4-methoxyphenyl)bismuth dichloride (2a): Yield
85%; m.p. 128–130 °C (lit. [3b], 135 °C); 1H NMR d 3.85
1
139–141 °C (lit. [24], 139–142 °C); H NMR d 7.56 (m,

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A.F.M. Mustafizur Rahman et al. / Journal of Organometallic Chemistry 689 (2004) 3395–3401
9H), 8.24 (m, 6H); 13C NMR d 129.59, 131.74, 134.11,
139.92.
THF (2 ml). Then a solution of triarylbismuth dichlo-
ride 2 or difluoride 3 (0.5 mmol) in the same solvent (1
ml) was added to the catalyst and the resulting mixture
was stirred at room temperature for 1 h. Filtration of
insoluble black substances deposited during the reaction
followed by concentration of the filtrate gave biaryl 4
(Yields are based on the formation of 0.75 mmol of 4).
4a: Yield 85% (0.64 mmol); m.p. 175–176 °C (lit. [26],
176–177 °C; 4b: Yield 85% (0.64 mmol); m.p. 70 °C (lit.
[26], 70–71 °C; 4c: Yield 90% (0.67 mmol); m.p. 146–147
°C (lit. [27], 147–148 °C); 4d: Yield 90% (0.67 mmol):
m.p. 111–112 °C (lit. [28], 110–112 °C; 4e: Yield 86%
(0.65 mmol); 83–84 °C (lit. [29], 82–87 °C); 4f: Yield
86% (0.65 mmol); m.p. 232–234 °C (lit. [27], 233–234
°C); 4g: Yield 86% (0.65 mmol); m.p. 235–237 °C (lit.
[30], 228–233 °C).
3.2. Synthesis of 3: general procedure
A mixture of triarylbismuth dichloride 2 (1 mmol) and
silver fluoride (2.4 mmol) was stirred in acetonitrile (5
ml) at room temperature for 1 h. The precipitated insol-
uble substances were filtered off and the filtrate was con-
centrated to leave an oily residue, which was crystallized
by an addition of hexane to give the product.
Tris(4-methoxyphenyl)bismuth difluoride (3a): Yield
1
86%; oil (lit. [10], oil); H NMR d 3.82 (s, 9H), 7.13
(d, 6H, J = 9.0 Hz), 8.09 (d, 6H, J = 9.0 Hz); Coupling
2
3
constants JCF and JCF could not be obtained since
the coupling of the fluorine atoms with the C1 and C2
atoms were not clearly observed.
Triphenylbismuth difluoride (3b): Yield 96%; m.p.
1
158–160 °C (lit. [13a], 158 °C); H NMR d 7.45 (t, 3H,
J = 8.2 Hz), 7.65 (t, 6H, J = 7.6 Hz), 8.22 (d, 6H,
Acknowledgement
J = 8.2 Hz).
Tris(4-chlorophenyl)bismuth difluoride (3c): Yield
90%; m.p. 68–70 °C (lit. [25], 97–103 °C); H NMR d
Support from the Japan Society for the Promotion of
Science (Grant-in-Aid for Scientific Research, No.
16550040) is gratefully acknowledged.
1
7.64 (d, 6H, J = 8.6 Hz), 8.14 (d, 6H, J = 8.6 Hz). Anal.
Calc. for C18H12BiCl3F2: C, 37.46; H, 1.99. Found: C,
37.12; H, 2.08%.
References
Tris(4-ethoxycarbonylphenyl)bismuth difluoride (3d):
1
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Yield 87%; m.p. 190–192 °C; H NMR d 1.40 (t, 9H,
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J = 7.2 Hz), 8.32 (d, 6H, J = 7.2 Hz); IR (cmꢀ1): 1725,
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Tris(4-trifluoromethylphenyl)bismuth difluoride (3e):
1
Yield 85%; m.p. 132–134 °C; H NMR d 7.94 (d, 6H,
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1578, 1524, 1474, 1389, 1008, 831. Anal. Calc. for
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1
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2 and 3: general procedure
Under argon, Pd(0) catalyst was prepared from
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