Synthesis and structure of 5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines

Article abstract of DOI:10.1016/j.jorganchem.2004.06.041

Hypervalent organobismuth compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines, with 13 different substituents on the bismuth atom including halogens, alkyl, alkenyl, alkynyl, aryl, or phenylthio groups have been synthesized. A key compound, 12-chloro-6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f] [1,5]azabismocine, which is a precursor for other azabismocines, has been synthesized by two different procedures; one is based on Akiba's method using 2-bromobenzylbromide as one of the starting materials and the other is a newly developed one using a cheaper starting material, 2-chlorobenzyl chloride. The structures of 12 new bismuth compounds were determined by X-ray diffraction. The eight-membered tetrahydroazabismocine ring has proved to be highly flexible and the hypervalent Bi - N bond distances vary ranging from 2.568(3) to 2.896(5) ?, depending on the electronic nature of the substituents on the bismuth atom. The Bi-N bond distances have good linear relationship against Hammett's m constants.

Full text of DOI:10.1016/j.jorganchem.2004.06.041

Journal of Organometallic Chemistry 689 (2004) 3012–3023
www.elsevier.com/locate/jorganchem
Synthesis and structure of
5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines
a,
a
b
Shigeru Shimada *, Osamu Yamazaki , Toshifumi Tanaka ,
b
Yohichi Suzuki , Masato Tanaka
a,c,
*
a
National Institute of Advanced Industrial Science and Technology, Tsukuba Central 5, 1-1-1 Higashi, Tsukuba, Ibaraki 305-8565, Japan
Department of Industrial Chemistry, College of Industrial Technology, Nihon University, 1-2-1 Izumi-cho, Narashino, Chiba 275-8575, Japan
b
c
Chemical Resources Laboratory, Tokyo Institute of Technology, 4259 Nagatsuta, Midori-ku, Yokohama 226-8503, Japan
Received 30 April 2004; accepted 24 June 2004
Available online 30 July 2004
Abstract
Hypervalent organobismuth compounds, 6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocines, with 13 different substitu-
ents on the bismuth atom including halogens, alkyl, alkenyl, alkynyl, aryl, or phenylthio groups have been synthesized. A key com-
pound, 12-chloro-6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine, which is a precursor for other azabismocines, has
been synthesized by two different procedures; one is based on Akibaꢀs method using 2-bromobenzylbromide as one of the starting
materials and the other is a newly developed one using a cheaper starting material, 2-chlorobenzyl chloride. The structures of 12
new bismuth compounds were determined by X-ray diffraction. The eight-membered tetrahydroazabismocine ring has proved to
˚
be highly flexible and the hypervalent Bi–N bond distances vary ranging from 2.568(3) to 2.896(5) A, depending on the electronic
nature of the substituents on the bismuth atom. The Bi–N bond distances have good linear relationship against Hammettꢀs rm
constants.
ꢀ 2004 Elsevier B.V. All rights reserved.
Keywords: Bismuth; Organobismuth compounds; Hypervalent; X-ray diffraction
1. Introduction
reaction with aryl bromides [3a] and aryl and alkenyl
chlorides [3b].
Bismuth compounds attract increasing interests as re-
agents as well as catalysts in organic synthesis [1]. We
have recently reported that organobismuth compounds
are useful reagents for the cross-coupling reaction with
organic halides and triflates [2,3]. In particular, hyperva-
lent organobismuth compounds, 6-tert-butyl-5,6,7,12-
tetrahydrodibenz[c,f][1,5]azabismocines 1, are highly
reactive and recoverable reagents for the cross-coupling
5,6,7,12-Tetrahydrodibenz[c,f][1,5]azabismocines were
first synthesized by Akiba and co-workers and their ba-
sic structural and chemical properties were reported [4].
They were also reported to act as antibacterial agents,
fungicides, algaecides, antifouling agents in a patent
[5]. Since we required a large amount of and various
types of compounds 1, following synthetic studies have
been done; (1) a new synthetic procedure for the con-
struction of 5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismo-
cine structure using cheaper starting materials and (2)
introduction of various groups on the bismuth atom of
5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine. In ad-
dition, the structures of 12 new bismuth compounds
have been determined by X-ray diffraction.
*
Corresponding author. Tel.: +81-298-614-588; fax: +81-298-614-
511.
E-mail address: s-shimada@aist.go.jp (S. Shimada).
0022-328X/$ - see front matter ꢀ 2004 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2004.06.041

S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
3013
R = tBu
X
tBu
cat. NaI
Et3N
1) Mg,
cat. FeCl2
6 (2 equiv)
+
tBuNH2
X
N
1b
F
3,4-(CH2O2)C6H3
1h
1a
DMF
2) BiCl3
Cl
Cl
1b Cl
1i 2,4,6-(MeO)3C6H2
CMe=CH2
1k C≡CPh
7
Br
I
1c
1d
1e
1f
1j
Scheme 2. Synthesis of 1b starting from 6.
C6F5
3,5-(CF3)2C6H3
Ph
Me
SPh
1l
1m
t
(Scheme 2). However, required (2-ClC6H4CH2)2 BuN
(7) was not obtained efficiently by the procedure for
t
the synthesis of 3, i.e., reaction of BuNH2 with 2 equiv
R
N
Bi X
1g
R = Me
X
X
of 6 in dmf at reflux in the presence of K2CO3; introduc-
tion of the second 2-chlorobenzyl group was slow and
the prolonged reaction resulted in the formation of a
large amount of by-products. The addition of a catalytic
amount of KI [7] improved the reactivity of 6 and gave 7
in 37% yield, while the formation of bis(2-chloro-
benzyl)carbonate became competitive to that of 7. The
use of stronger base, NaH, did not afford 7 at all, instead
resulted in the formation of trans-1,2-bis(2-chlorophe-
nyl)ethene in 54% yield. Finally we found that the use
of Et3N as a base in the presence of a catalytic amount
of NaI afforded 7 in 70–84% isolated yields (four runs in
0.04–1.5 mol scales were performed).
2a
2b
2c
2d
F
Cl
I
2e 4-(CF3)C6H4
4-MeC6H4
2g Me
2f
Ph
2. Results and discussion
2.1. Syntheses
Akiba and co-workers synthesized the key com-
pound 2b, which was a precursor for other compounds
2a and 2c–2g, by the reaction of BiCl3 and (2-
LiC6H4CH2)2MeN. The latter compound was in situ
Formation of di-Grignard reagent from 7 did not
proceed at all by the usual procedure, but was accom-
plished in a high yield by using a catalytic amount of
n
´
FeCl2 as reported by Bogdanovic and Schwickardi [8].
generated by the reaction of 2 equiv of BuLi and (2-
Fe(acac)2 similarly worked albeit slightly less efficient
than FeCl2. Subsequent reaction with BiCl3 afforded
1b in 41–62% isolated yields (five runs in 0.007–0.23
mol scales were performed). This new procedure using
cheaper starting material and reagent is probably appli-
cable not only to bismuth compounds but also to related
compounds of silicon [6,9], phosphorous [10], anti-
mony[4a,9], sulfur [11], selenium[12], tellurium[13], and
zirconium [14].
Synthesis of other halogen derivatives 1a, 1c and 1d
was first examined by the halogen exchange reaction us-
ing an excess of NaX (Scheme 3). Conversion of 1b to 1c
or 1d was almost quantitative and pure 1c and 1d were
obtained in more than 90% yields. On the other hand,
conversion of 1b to fluoride 1a was about 40% even
100 equiv of NaF was used, and isolation of 1a was
not successful. However, treatment of 1b with 2 equiv
of Bu4NF in thf afforded 1a nearly quantitatively, al-
though again the isolation of 1a in pure form was not
successful because 1b easily regenerated during isolation
process. The procedure used for the synthesis of fluoride
2a (KF in dmf) by Akiba was also unsuccessful for the
synthesis of 1a [4a]. Finally we succeeded in isolating
BrC6H4CH2)2MeN (3), which in turn was prepared
from 2-BrC6H4CH2Br (4) and MeNH2. A similar pro-
cedure is applicable to 1b by using (2-BrC6-
t
H4CH2)2 BuN 5 (Scheme 1), which was prepared from
t
4 and BuNH2 and used for the synthesis of related sil-
icon compounds by Corriu and co-workers [6]. The re-
t
action of BiCl3 and (2-LiC6H4CH2)2 BuN in situ
generated from 5 afforded 1b in 65–80% isolated yields
(four runs in 29–100 mmol scales were performed).
However, it became clear that 1b obtained by this pro-
cedure was contaminated with a small amount (ꢀ10%)
of bromide 1c; the latter compound probably arose
from the metathesis of 1b with in situ generated LiBr
or derived from BiClnBr3 ꢁ n (n = 0–2) formed by the
metathesis of BiCl3 and LiBr. The amount of contami-
nant 1c in 1b could be reduced by treatment with aque-
ous NH4Cl or HCl solution.
Since one of the starting materials, 4, is rather expen-
sive compound, we examined to use a much cheaper
starting material, 2-ClC6H4CH2Cl 6, instead of 4, which
also expected to exclude the bromide contamination
tBu
1) 2 nBuLi
N
1b
1b
NaX
1a or 1c or 1d
+
2) BiCl3
CH2Cl2 / H2O
X = F, Br, I
excess
Br
Br
5
Scheme 1. Synthesis of 1b from 5.
Scheme 3. Halogen exchange reaction of 1b.

3014
S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
pure 1a by the reaction of phenyl compound 1g (vide in-
fra) with an excess of a dilute aqueous HF solution. Io-
dide 1d was also obtained by the reaction of 1g with I2,
which is expected to proceed through pentavalent bis-
muth intermediate that forms 1d and PhI [15].
Isolation of the products was generally easily per-
formed by recrystallization, Al2O3 column chromatog-
raphy or solvent extraction. However, the isolation of
1i was rather troublesome because 1i was not stable to
chromatography (silica gel, alumina, florisil) and the
separation of a by-product, 1,3,5-trimethoxybenzene,
was not easy and impure 1i did not crystallize easily.
Therefore, 1i was isolated only in a low yield by repeated
fractional solvent extraction and fractional precipitation
procedure.
Halides 1a–1d are stable to air and can be stored un-
der air. Aryl-, alkenyl-, alkynyl-, and alkyl-substituted
compounds 1e–1l in the solid state can be handled under
air for hours without noticeable change, but are less sta-
ble to air than halides 1a–1d and should be stored under
an inert atmosphere.
Introduction of organic groups on the bismuth atom
of 5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismocine was
accomplished by the reaction of 1b with organolithium
reagents as reported by Akiba and co-workers [4] or with
Grignard reagents (Table 1, entries 1–10). Similarly, PhS
group was easily introduced by the reaction of 1b with
PhSLi to give 1m (Table 1, entry 11). In two cases, i.e.,
for 1g and 1l, both of organolithium and Grignard rea-
gents were tested. In both cases, organolithium reagents
afforded the desired products in higher yields than Grig-
nard reagents (Table 1, entries 3–4 and 9–10). When 1h
was synthesized by the reaction of 1b with commercial
3,4-(CH2O2)C6H4MgBr, once 1h was produced in a good
yield as judged by 1H NMR analysis. However, the
amount of 1h decreased with the formation of bromide
1c during prolonged reaction and/or work-up process.
This is probably because 1h reacted with ‘‘MgBrX’’
(X = Cl or Br) generated during the reaction to form
1c; indeed a separate experiment showed that 1h reacted
with MgBr2 Æ OEt2 in thf-d8 to form bromide 1c in ca.
30% yield after heating at 50 ꢁC for 3 h, although the re-
sulting magnesium species was not identified. Phenyl
compound 1g is less reactive to MgBr2 Æ OEt2 and gave
1c in 5% yield after heating at 80 ꢁC for 3 h. The reactiv-
ity difference between 1h and 1g toward MgBr2 Æ OEt2
agrees well with the difference in their yields obtained
by the reaction of 1b with Grignard reagents (Table 1,
entries 4–5).
2.2. Molecular structure
Existence of hypervalent bonds in 5,6,7,12-tetrahyd-
rodibenz[c,f][1,5]azabismocines was confirmed by Akiba
and co-workers [4] through the NMR spectroscopy of
2a–2g in solution as well as single crystal X-ray analysis
1
of 2e and 2f in the solid state. H and 13C NMR chem-
ical shifts of the methyl group on nitrogen in 2a–2d and
2g largely affected by the substituents on the bismuth at-
om (i.e., F, Cl, I, Ph and Me) and showed linear rela-
tionship against Hammettꢀs rm constants of the
substituents [4a]. This result suggests that the transannu-
lar bonds are flexible and affected by the substituents on
the bismuth atom. Indeed, X-ray analysis of 2e and 2f
showed that the Bi–N bond distances were influenced
by the electronic nature of the substituents [4b].
In order to obtain more detailed information on the
structure of 5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismo-
cines, we have determined the structures of 12 com-
pounds, 1a–1e and 1g–1m, by single crystal X-ray
analysis. Selected bond distances and angles are summa-
rized in Table 2.
An alternative method for the preparation of 1e–1l is
t
the reaction of RBiX2 with (2-LiC6H4CH2)2 BuN.
RBiX2 can be obtained by metathesis of R3Bi and 2
equiv of BiX3 [16]. The reaction of PhBiBr2 with (2-
t
LiC6H4CH2)2 BuN efficiently proceeded to afford 1g in
97% yield.
˚
Bi–N distances range from 2.568(3) to 2.896(5) A. As
shown in Fig. 1, Bi–N distances have good linear rela-
tionship against Hammettꢀs rm constants [17] of the sub-
Table 1
Synthesis of 1e–1m
1
stituents on the bismuth atom as observed for the H
and 13C NMR chemical shifts by Akiba (from [17],
Hammettꢀs rm constants are available for 9 compounds
among the 12 compounds analyzed by X-ray).
1b þ RLi or RMgX or PhSLi ! 1e–1m
RM
Entry
Product
Yielda (%)
1
2
C6F5Li
1e
1f
66
76
81
65
24
17
74
85
89
15
64
Halides 1a–1d are monomeric in the solid state, al-
though 1a was obtained as a hydrate and two molecules
of 1a were connected each other through hydrogen
bonds between H2O molecules and F atoms (Fig.
2(a)). Structurally characterized bismuth fluorides are
limited and seven examples are found in the Cambridge
Structural Database (CSD) [4b,18,19], and one example
was recently reported [20]. Among them only one is
Bi(III) [19a] and the others are Bi(V) compounds includ-
ing pentavalent derivatives of 2e and 2f. The reported
3,5-(CF3)C6H3Li
PhLi
PhMgBr
3
1g
1g
1h
1i
4
5
3,4-(CH2O2)C6H3MgBr
2,4,6-(MeO)3C6H2Li
CH2‚C(Me)MgBr
PhC„CLi
6
7
1j
8
1k
1l
9
MeLi
MeMgBr
PhSLi
10
11
1l
1m
a
Isolated yield.

Table 2
˚
Selected bond distances (A) and angles (ꢁ) for compounds 1a–1e and 1g–m
X
d
b
c
Bi
C1
C2
a
f
e
N
g
tBu
Bond or angle
1a
1b
1c
1d
1e
1ga
1h
1i
1j
1k
1l
1ma
a
2.574(4)
2.246(6)
2.234(6)
2.190(4)
72.6(2)
2.568(3)
2.241(3)
2.250(5)
2.663(1)
75.1(1)
2.559(4)
2.247(5)
2.247(5)
2.569(3)
2.254(4)
2.256(4)
3.0139(3)
74.7(1)
2.700(5)
2.244(6)
2.265(6)
2.349(6)
72.5(2)
2.836(6)
2.270(8)
2.284(8)
2.286(8)
70.0(2)
2.823(6)
2.277(7)
2.269(7)
2.306(7)
69.2(2)
2.875(4)
2.258(4)
2.263(4)
2.293(4)
69.5(1)
69.3(1)
154.0(1)
99.3(1)
92.4(1)
96.6(2)
98.6(2)
98.2(2)
121.6(3)
2.826(5)
2.243(7)
2.262(7)
2.306(7)
70.3(2)
2.740(2)
2.252(4)
2.257(3)
2.289(4)
71.7(1)
2.894(4)
2.275(7)
2.266(6)
2.264(6)
69.3(2)
68.8(2)
150.4(2)
98.1(2)
91.3(2)
93.3(2)
99.9(3)
98.9(3)
119.9(4)
2.669(4)
2.256(4)
2.251(4)
2.634(1)
72.1(1)
b
c
d
2.7912(5)
75.3(1)
72.9(1)
ab
ac
ad
bc
bd
cd
ae
af
74.9(2)
73.1(1)
73.0(1)
161.06(7)
95.6(1)
71.1(2)
69.6(2)
69.5(2)
68.8(2)
70.1(1)
72.0(1)
153.6(2)
94.6(2)
88.7(2)
158.73(9)
93.6(1)
90.8(1)
159.83(9)
93.9(2)
91.4(1)
153.4(2)
99.5(2)
90.2(2)
153.3(2)
97.6(3)
93.1(3)
152.4(2)
99.0(2)
91.9(3)
151.9(2)
99.2(3)
90.5(3)
153.6(1)
91.2(1)
90.9(1)
155.53(8)
97.0(2)
93.3(1)
93.36(9)
94.02(9)
104.7(2)
101.9(2)
115.2(2)
88.6(2)
92.4(1)
93.4(1)
92.9(2)
93.5(3)
95.0(2)
95.6(3)
91.2(1)
91.1(1)
101.6(3)
104.4(3)
115.9(3)
105.0(2)
102.3(2)
114.2(2)
105.0(3)
102.2(3)
113.9(3)
102.2(3)
102.1(3)
116.0(4)
100.5(4)
101.9(4)
116.6(5)
101.3(4)
100.3(4)
116.8(4)
101.7(3)
101.8(4)
115.8(4)
104.3(2)
100.1(2)
114.1(2)
1.195(5) (C„C)
102.2(2)
102.1(2)
115.9(3)
101.3(2) (Bi–S–C)
ag
others
a
Average values of two independent molecules in the unit cell are shown.

3016
S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
chelating N–Bi–C2 angles (86.5(2)–89.0(2)ꢁ) in 8a–8c are
much wider than the chelating one (73.1(1)ꢁ) in 1b, other
important bond lengths and angles have good similarity
˚
(for 8a–8c, Bi–N 2.525(6)–2.570(5) A and Bi–Cl
˚
2.634(6)–2.700(2) A, N–Bi–Cl 161.7(4)–165.1(1)ꢁ, N–
Bi–C1 72.0(6)–72.7(7)ꢁ and C1–Bi–C2 93.7(2)–98.0(8)ꢁ).
Structural similarity is also observed between iodides
1d and 9, the latter has a non-chelating 4-methylpyridine
ligand [22]. Structural parameters of 1d and 9 are very
1
˚
˚
similar (for 9, Bi–N 2.604(7) A, Bi–I 3.0229(8) A, C –
Bi–C2 96.2(3)ꢁ, C1–Bi–I 90.8(2)ꢁ, C2–Bi–I 94.2(2)ꢁ)
except for N–Bi–I 174.2(2)ꢁ, N–Bi–C1 86.8(2)ꢁ and N–
Bi–C2 80.8(2)ꢁ; the eight-membered ring in 1d forces
the nitrogen atom deviate from the axial position of trig-
onal bipyramidal geometry. This structural similarity
suggests that the eight-membered tetrahydroazabismo-
cine ring are quite flexible and therefore the Bi–N bond
distances well reflect the nature of the substituents on
the bismuth centers.
Fig. 1. Relationship between Bi–N hypervalent bond distances and
Hammettꢀs rm constants.
I
Cl
R2
Bi
Bi
C1
C2
C1
C2
R1
N
Me2N
R3
8a: R1 = R3 =Me, R2 = H
8b: R1 = R2 =H, R3 = Me
8c: R1 = R3 =H, R2 = CH2NMe2
Me
9
Molecular structure of 1e, 1j, 1k and 1l are shown in
Figs. 3–6, respectively. The structural parameters of
12-oraganyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismo-
cines 1e–1l are very similar to those of 2e and 2f [4b], al-
though C1–Bi–C2 angles of 1e–1l (91.2(1)–99.5(2)ꢁ) are
smaller than those of 2e and 2f (101.7(1)–102.3(2)),
Fig. 2. Molecular structure of (a) 1a ꢂ H2O and (b) 1b. Thermal
ellipsoids are drawn at 50% probability. Hydrogen atoms were omitted
for clarity.
˚
Bi–F distances range from 2.088(8) to 2.222(4) A except
those of (C14H9)3BiF2 [19c] and Ph3BiF2 [19d], which
˚
are considerably long (2.498(8) and 2.53(1)–2.59(1) A,
˚
respectively). The Bi–F distance of 1a, 2.190(4) A, is
within the normal range.
The structure of chloride 1b (Fig. 2(b)) has good sim-
ilarity to those of bismuth clorides 8a–8c [21] that have
(2-dimethylaminomethyl)phenyl ligands. Although non-
Fig. 3. Molecular structure of 1e. Thermal ellipsoids are drawn at 50%
probability. Hydrogen atoms were omitted for clarity.

S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
3017
˚
distance in 1k (2.289(4) A) is longer than those in three
alkynyl bismuth compounds found in CSD (2.151(8)–
˚
2.249(6) A) [15,18,23].
3. Conclusions
A new procedure for the construction of 5,6,7,12-
tetrahydrodibenz[c,f][1,5]azabismocine structure using
cheaper starting materials has been developed. Introduc-
tion of various organic groups on the bismuth atom of
6-tert-butyl-5,6,7,12-tetrahydrodibenz[c,f][1,5]azabismo-
cine can be accomplished by organolithium or Grignard
reagents, although the latters are sometimes not very
suitable depending on the organic groups to be intro-
duced. The X-ray structure determination of 12 new
compounds has proved that the eight-membered tetra-
hydroazabismocine rings are highly flexible and the
hypervalent Bi–N bond distances are in good linear rela-
tionship against Hammettꢀs rm constants of the substit-
uents on the bismuth atom.
Fig. 4. Molecular structure of 1j. Thermal ellipsoids are drawn at 50%
probability. Hydrogen atoms were shown only for the isopropenyl
group for clarity.
4. Experimental
4.1. General
All manipulations of air-sensitive materials were car-
ried out under a nitrogen atmosphere using standard
Schlenk tube techniques or in a glovebox filled with ar-
gon. Et2O and thf were distilled from Na/benzophenone
ketyl. All other anhydrous solvents were purchased from
Kanto Chemicals or Aldrich and used as received. BiCl3
was purified by reluxing with SOCl2 and sublimation
under vacuum. Magnesium powder (ꢀ45 lm, 99.5%)
was purchased from Wako Pure Chemical Industries.
3,4-CH2O2C6H4MgBr and CH2‚C(Me)MgBr were
purchased from Aldrich and used as received. 2,4,6-
(MeO)3C6H2Li was prepared as described in the litera-
Fig. 5. Molecular structure of 1k. Thermal ellipsoids are drawn at 50%
probability. Hydrogen atoms were omitted for clarity.
1
ture [24]. H, 13C and 19F NMR spectra were recorded
on Jeol LA500 spectrometer. Chemical shifts given in
1
ppm are referenced to tetramethylsilane for H NMR
spectra (0.0 ppm), to solvent signal (CDCl3) for 13C
NMR spectra (77.0 ppm) and to C6H5CF3 for 19F
NMR spectra (ꢁ63.72 ppm) and coupling constants
were reported in hertz.
t
4.2. Preparation of Bu(2-ClC6H4CH2)2N (7)
Fig. 6. Molecular structure of 1l. Thermal ellipsoids are drawn at 50%
probability. Hydrogen atoms were omitted for clarity.
To a mixture of tBuNH2 (112 g, 1.53 mol), Et3N (600
ml, 4.3 mol), and NaI (2.81 g, 18.7 mmol) in dmf (700
ml) was added 2-ClC6H4CH2Cl (512 g, 3.18 mol) drop-
wise under N2. The mixture was gradually warmed to 85
ꢁC and stirred for 15 h at this temperature. Then the
temperature was raised to 120 ꢁC and stirred for 50 h.
After cooling to room temperature, Et2O (1.7 l) and
which may reflect the difference of the substituents on
the nitrogen atom. The exocyclic Bi–C distances in
1e–1l do not simply reflect the difference of electronic
properties of Csp, Csp2 and Csp3 atoms. The Bi–Csp

3018
S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
water (800 ml) were added. Organic layer was separated,
dried over Na2SO4, and concentrated under vacuum.
The residue was passed through a short silica gel column
(hexane/EtOAc = 20/1) and then recrystallized from
hexane to give 7 as colorless solid (348 g, 71%); m.p.
passed through a silica gel column (300 g) to remove
deep brown-colored materials. The eluent was evaporated
to give crude 1b, which was recrystallized from CH2Cl2/
hexane to give pure 1b as colorless crystals (46.6 g, 41%);
m.p. 265–266 ꢁC. 1H NMR (CDCl3, 499.1 MHz): d 1.29
(9H, s), 4.10 (2H, d, J = 15.5), 4.49 (2H, d, J = 15.5),
7.29 (2H, t, J = 7.5), 7.40 (2H, d, J = 7.5), 7.44 (2H, d,
J = 7.5), 8.62 (2H, d, J = 7.5). 13C NMR (CDCl3,
125.4 MHz): d 27.73 (CH3), 60.09 (C(CH3)3), 60.26
(CH2), 127.47, 128.21, 130.69, 138.24, 151.16 (CCH2),
170.88 (CBi). Calc. for C18H21BiClN: C, 43.60; H,
4.27; N, 2.83. Found: C, 43.31; H, 3.89; N, 2.67%.
1
83–84 ꢁC. H NMR (CDCl3, 499.1 MHz): d 1.20 (9H,
s), 3.85 (4H, s), 6.96 (2H, dt, J = 1.5, 7.5), 7.04 (2H,
dt, J = 1.0, 7.5), 7.13 (2H, dd, J = 7.5, 1.0), 7.52 (2H,
dd, J = 7.5, 1.5). 13C NMR (CDCl3, 125.4 MHz): d
26.99 (CH3), 51.37 (CH2), 56.07 (C(CH3)3), 126.03,
127.26, 128.76, 130.83, 132.99, 139.09. Calc. for
C18H21Cl2N: C, 67.08; H, 6.57; N, 4.35. Found: C,
67.22; H, 6.54; N, 4.30%.
4.4. Preparation of [tBuN(CH2C6H4)2BiF] (1a)
4.3. Preparation of [tBuN(CH2C6H4)2BiCl] (1b)
To a CH2Cl2 solution (5 ml) of phenylbismuth com-
pound 1g (109 mg, 0.20 mmol) was added a 0.58 M
aqueous HF solution (3.5 ml, 2.0 mmol) at room tem-
perature and the resulting mixture was stirred for 3 h
at the same temperature. After the addition of 1 M
aqueous NH4F solution (5 ml) and CH2Cl2 (10 ml),
the organic layer was separated, washed with water,
and dried over anhydrous Na2SO4. NMR analysis of
the crude mixture showed quantitative formation of
1a. Recrystallization from CH2Cl2/hexane mixture af-
forded colorless crystals of 1a (75 mg, 75%), which
was proved to contain one molecule of water per 1a
by the single crystal X-ray analysis; m.p. 171–172 ꢁC.
1H NMR (CDCl3, 499.1 MHz): d 1.29 (9H, s), 4.06
(2H, d, J = 15.5), 4.46 (2H, d, J = 15.5), 7.25 (2H, dt,
J = 1.0, 7.5), 7.39 (2H, d, J = 7.5), 7.49 (2H, t,
J = 7.5), 8.17 (2H, br, s). 13C NMR (CDCl3, 125.4
MHz): d 27.50 (CH3), 59.51 (C(CH3)3), 60.12 (CH2),
127.53, 127.93, 129.94, 135.46, 150.91 (CCH2), 177.57
(CBi). 19F NMR (CDCl3, 469.6 MHz): d ꢁ188.70. Calc.
for C18H23BiFNO (1a Æ H2O): C, 43.47; H, 4.66; N, 2.82.
Found: C, 43.43; H, 4.21; N, 2.70%.
From 3: To an Et2O (250 ml) solution of amine 3
(41.11 g, 100 mmol) was added a hexane solution of
nBuLi (1.55 M, 128 ml, 198 mmol) at ꢁ30 ꢁC. The mix-
ture was gradually warmed to room temperature over
3 h and then added to a mixture of BiCl3 (31.76 g, 101
mmol) in Et2O (750 ml) at ꢁ78 ꢁC. The mixture was
gradually warmed to room temperature over 8 h and
then continued to stir for 7 h at room temperature. Most
of the solvent was removed under vacuum and the resi-
due was poured into a mixture of CHCl3 (800 ml) and
aqueous NH4Cl solution (1 M, 400 ml). Organic layer
was separated, dried over Na2SO4, filtered through Cel-
ite. The filtrate was concentrated to one third of the
original volume and hexane (500 ml) was added to pre-
cipitate 1b (34.54 g) as colorless crystals. Additional 1b
(5.18 g) was obtained from the residue by silica gel col-
umn chromatography (CH2Cl2). Total yield: 39.71 g
(80%). The purity of 1b at this stage was ca. 97% by
1H NMR spectroscopy with ca. 3% of bromide 1c. Re-
crystallization from CH2Cl2/hexane mixture afforded
pure 1b. From 7. Magnesium powder (20 g, 0.82 mol)
was treated with a tiny piece of I2 in thf (50 ml) at room
temperature. After the disappearance of I2 color, Et-
MgCl (2.0 M in thf, 14 ml, 28 mmol) was added and
the mixture was heated to 65 ꢁC. To the mixture was
added FeCl2 (1.74 g, 13.7 mmol), MgCl2 (0.50 M in
thf, 28 ml, 14 mmol), and then amine 7 (88.6 g, 0.275
mol) in thf (100 ml) over 25 min at the same tempera-
ture. The mixture was stirred for 1 day at 65 ꢁC and fil-
tered through Celite to remove unreacted magnesium
after cooling to room temperature. The solution was
added dropwise to a mixture of BiCl3 (72.3 g, 0.229
mol) in thf (800 ml) at ꢁ30 ꢁC over 1 h. The mixture
was gradually warmed to room temperature and stirred
for 1 day. Then the mixture was treated with water (50
ml), filtered, and evaporated. The residue was dissolved
in CH2Cl2 (700 ml), washed with aqueous HCl (1 M, 200
ml) and dried over Na2SO4. After evaporation of the
solvent, the residue was dissolved in CH2Cl2 (300 ml),
4.5. Preparation of [tBuN(CH2C6H4)2BiBr] (1c)
Chloride 1b (100 mg, 0.202 mmol) and NaBr (500 mg,
4.86 mmol) were dissolved in a mixture of CH2Cl2/H2O
(10 ml/10 ml) and stirred for 3 h at room temperature.
The organic layer was separated and dried over Na2SO4.
Removal of the solvent under vacuum gave 99.7 mg
(92%) of 1c as a white solid; m.p. 238–239 ꢁC. 1H
NMR (CDCl3, 499.1 MHz): d 1.30 (9H, s), 4.11 (2H,
d, J = 15.5), 4.49 (2H, d, J = 15.5), 7.32 (2H, t, J = 7),
7.40 (2H, d, J = 7), 7.43 (2H, t, J = 7), 8.77 (2H, d,
J = 7). 13C NMR (CDCl3, 125.4 MHz): d 27.71 (CH3),
60.12 (CH2), 60.15 (C(CH3)3), 127.26, 128.18, 130.91,
140.02, 151.09, 167.43 (CBi). Calc. for C18H21BiBrN:
C, 40.02; H, 3.92; N, 2.59. Found: C, 40.16; H, 3.77;
N, 2.52%.

S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
3019
4.6. Preparation of [tBuN(CH2C6H4)2BiI] (1d)
4.8. Preparation of [tBuN(CH2C6H4)2Bi{3,5-(CF3)2-
C6H3}] (1f)
From 1b: Chloride 1b (100 mg, 0.202 mmol) and NaI
(500 mg, 3.34 mmol) were dissolved in a mixture of
CH2Cl2/H2O (10 ml/10 ml) and stirred for 3 h at room
temperature. The organic layer was separated and dried
over Na2SO4. Removal of the solvent under vacuum
gave 109 mg (93%) of 1d as a light yellow solid. From
1g: To a solution of 1g (2.02 g, 3.75 mmol) in Et2O
(10 ml) was added I2 (922 mg, 3.63 mmol) at room tem-
perature. The colour of I2 disappeared quickly and solid
precipitated. After stirring at room temperature for 30
min, liquid portion was removed by syringe and the re-
maining solid was washed with Et2O (2 · 10 ml). Re-
crystallization from toluene gave 1.69 g (79%) of 1d as
An Et2O solution of 3,5-(CF3)2C6H3Li was prepared
by the addition of 1.55 M hexane solution of nBuLi
(10.2 ml, 15.8 mmol) to a solution of 3,5-(CF3)2C6H3Br
(2.8 ml, 16 mmol) in 20 ml of Et2O at ꢁ80 ꢁC and
gradual warming of the resulting solution to 10 ꢁC.
18 ml of the above solution was added to a solution
of 1b (4.0 g, 8.1 mmol) in 80 ml of Et2O at ꢁ80 ꢁC.
The mixture was stirred overnight with gradual warm-
1
ing to room temperature. H NMR analysis of the re-
action mixture indicated that 1f was formed almost
quantitatively. After removal of solvent under reduced
pressure, the residue was extracted with CH2Cl2 (30
ml). The extract was filtered through Celite, which
was washed with toluene (10 ml). The combined filtrate
was evacuated to reduce the volume to 10 ml to give
white precipitates. Removal of the supernatant by de-
cantation, washing the residual solid with hexane
(3 · 15 ml), and drying under vacuum afforded 3.18 g
of 1f (58%). From the supernatant was obtained anoth-
er crop of 1f (0.97 g, 18%) by reducing the volume un-
1
light yellow-orange crystals; m.p. > 300 ꢁC. H NMR
(CDCl3, 499.1 MHz): d 1.32 (9H, s), 4.08 (2H, d,
J = 15.5), 4.44 (2H, d, J = 15.5), 7.36–7.41 (6H, m),
9.00–9.03 (2H, m) 13C NMR (CDCl3, 125.4 MHz): d
27.83 (CH3), 59.77 (CH2), 60.26 (C(CH3)3), 127.01,
128.28, 131.50, 144.00, 151.04, 161.08 (CBi). Calc. for
C18H21BiIN: C, 36.81; H, 3.60; N, 2.39. Found: C,
36.80; H, 3.33; N, 2.24%.
1
der vacuum; m.p. 218–221 ꢁC. H NMR (CDCl3, 499.1
MHz): d 1.23 (9H, s), 3.90 (2H, d, J = 15.5), 4.23 (2H,
d, J = 15.5), 7.12 (2H, td, J = 7.0, 1.8), 7.22–7.27 (4H,
m), 7.41 (2H, d, J = 7.5), 7.86 (1H, s), 8.30 (2H, s).
13C NMR (CDCl3, 125.4 MHz): d 27.35 (CH3), 56.81
(CH2), 57.82 (C(CH3)3), 121.11 (septet, JC – F = 4),
1
124.05 (q, JC – F = 273, CF3), 127.78, 127.92, 129.30,
2
131.58 (q, JC – F = 32, CCF3), 138.65, 139.49, 149.36
4.7. Preparation of [tBuN(CH2C6H4)2BiC6F5] (1e)
To a solution of C6F5Li in an Et2O/hexane mixture,
n
prepared from C6F5Br (0.50 ml, 4.0 mmol) and BuLi
3
in hexane (1.58 M in hexane, 2.5 ml, 4.0 mmol) in
Et2O (15 ml) at ꢁ78 ꢁC, was added 1b (2.0 g, 4.0 mmol)
at ꢁ78 ꢁC, and the mixture was stirred overnight with
gradual warming to room temperature to form white
suspension. The solid was separated by filtration
through Celite and the filtrate was concentrated in va-
cuo. The residual solid was recrystallized from Et2O
(10 ml) to form pure crystals of 1e (1.09 g, 43%). The
separated solid by the above Celite filtration was washed
with CH2Cl2 to extract remaining 1e. The CH2Cl2 solu-
tion was concentrated under vacuum and the resulting
solid was recrystallized from Et2O to give additional
1e (0.58 g, 23%). Concentration of combined liquid
parts of two recrystallizations afforded 0.38 g of solid
mainly consisting of 1e; m.p. 149–152 ꢁC. 1H NMR
(CDCl3, 499.1 MHz): d 1.24 (9H, s), 3.99 (2H, d,
J = 15.5), 4.29 (2H, d, J = 15.5), 7.17 (2H, dt, J = 1.5,
7.5), 7.27 (2H, dt, J = 1.0, 7.5), 7.31 (2H, dd, J = 1.0,
7.5), 7.80 (2H, d, J = 7.5). 13C NMR (CDCl3, 125.4
MHz): d 27.51, 57.43, 58.38, 127.71, 127.90, 129.55,
135.9–138.3 (a pair of multiplets, C–F), 139.84, 139.8–
142.1 (a pair of multiplets, C–F), 146.7–148.9 (a pair
of multiplets, C–F), 149.61, 154.49, 169.98. 19F NMR
(CDCl3, 469.6 MHz): d ꢁ160.40 (m), ꢁ154.86 (t,
J = 19), ꢁ115.08 (m). Calc. for C24H21BiF5N: C,
45.94; H, 3.37; N, 2.23. Found: C, 46.10; H, 3.19; N,
2.13%.
(CCH2), 153.08 (CBi), 167.84 (CBi). Calc. for
C26H24BiF6N: C, 46.37; H, 3.59; N, 2.08. Found: C,
46.46; H, 3.33; N, 2.00%.
4.9. Preparation of [tBuN(CH2C6H4)2BiPh] (1g)
To a suspension of 1b (10.0 g, 20.2 mmol) in Et2O
(200 ml) was added dropwise a cyclohexane/Et2O
(3/1) solution of PhLi (0.41 M, 50 ml, 21 mmol) over
30 min at ꢁ78 ꢁC under nitrogen. After stirring at
the same temperature for 30 min, the mixture was al-
lowed to warm to room temperature by removing the
1
cooling bath and stirred for 1 day. H NMR analysis
of the reaction mixture showed complete consumption
of 1b and nearly quantitative formation of 1g. The
mixture was filtered through Celite and the filtrate
was evaporated to remove volatiles. The residue was
dissolved in a CH2Cl2/hexane (5 ml/40 ml) mixture
and filtered through Celite. After removal of volatiles
under vacuum, the residual solid was recrystallized by
dissolving in a CH2Cl2/Et2O (2.5 ml/25 ml) mixture, re-
ducing the volume of the mixture to ca. 10 ml, and the
addition of hexane (10 ml) to give colorless crystal of
1
1g (8.81 g, 81%); m.p. 125–126 ꢁC. H NMR (CDCl3,
499.1 MHz): d 1.22 (9H, s), 3.85 (2H, d, J = 15.5), 4.18

Table 3
Crystal data, data collection and refinement parameters for compounds 1a–1e and 1g–1m
1a
1b
1c
1d
1e
1g
Formula
C18H21BiFN Æ H2O
497.36
C18H21BiClN
495.80
C18H21BiBrN
540.26
C18H21BiIN
587.26
C24H21BiF5N
627.41
C24H26BiN
537.46
Formula weight
Crystal size
Crystal system
Space group
0.30 · 0.15 · 0.10
Triclinic
0.18 · 0.11 · 0.04
Monoclinic
P21/n (#14)
9.8378(9)
0.25 · 0.22 · 0.13
Monoclinic
P21/n (#14)
9.9307(7)
0.20 · 0.20 · 0.05
Monoclinic
P21/c (#14)
12.333(1)
0.20 · 0.20 · 0.15
Monoclinic
Cc (#9)
0.55 · 0.30 · 0.20
Triclinic
ꢀ
ꢀ
P1 (#2)
P1 (#2)
˚
a (A)
10.390(1)
10.5484(9)
9.342(1)
101.75(1)
113.06(1)
106.701(9)
842.2(2)
2
9.543(2)
21.834(1)
11.020(1)
10.176(3)
12.588(5)
17.295(4)
92.85(3)
92.15(2)
109.28(3)
2085(1)
4
˚
b (A)
16.072(1)
11.3655(8)
16.335(1)
11.3634(7)
9.555(2)
14.882(2)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
109.951(6)
109.914(4)
92.266(9)
105.310(9)
˚
V (A)
1689.1(2)
4
1.95
1733.1(2)
4
2.07
1752.4(4)
4
2.23
2214.8(4)
4
1.88
Z
Dcalc (g cmꢁ3
F(0 0 0)
)
1.96
476.00
1.71
944.00
105.71
153(2)
x–2h
55.0
4207
1016.00
124.61
193(2)
x–2h
55.0
4307
1088.00
118.00
153(2)
x–2h
55.0
4466
1200.00
79.98
1040.00
84.47
193(2)
l (Mo Ka) (cmꢁ1
T (K)
Scan type
)
104.60
173(2)
193(2)
x–2h
55.0
x–2h
55.0
4081
x–2h
55.0
9998
2hmax (ꢁ)
Number of reflections measured
Number of unique reflections
Number of variables
R1 (I0 > 2.0r(I0))
2766
4076 (Rint = 0.012)
199
0.042
3871 (Rint = 0.022)
212
0.022
3962 (Rint = 0.017)
191
0.027
4029 (Rint = 0.013)
212
0.022
2692 (Rint = 0.089)
302
0.020
9558 (Rint = 0.027)
469
0.035
wR2 (all data)
Goodness-of-fit
˚
Differential peak, hole (e A
0.109
1.51
0.059
1.02
0.083
1.05
0.052
1.00
0.043
1.04
0.134
1.15
ꢁ3
)
4.46, ꢁ5.42
1.53, ꢁ1.35
2.07, ꢁ1.48
1.43, ꢁ1.49
1.35, ꢁ1.26
1.68, ꢁ2.69
1h
1i
1j
1k
1l
1m
Formula
C25H26BiNO2
581.47
C27H32BiNO3
627.54
C21H26BiN
501.42
C26H26BiN
561.48
C19H24BiN
475.39
C24H26BiNS
569.52
Formula weight
Crystal size
Crystal system
Space group
0.30 · 0.23 · 0.15
Monoclinic
P21/c (#14)
9.095(5)
0.22 · 0.12 · 0.27
Orthorhombic
Pbca (#61)
20.816(3)
0.40 · 0.30 · 0.20
Orthorhombic
P212121 (#19)
12.747(3)
0.14 · 0.04 · 0.02
Monoclinic
P21/c (#14)
9.5606(4)
0.35 · 0.13 · 0.04
Monoclinic
P21/c (#14)
14.165(1)
0.40 · 0.40 · 0.15
Monoclinic
P21/n (#14)
20.817(3)
˚
a (A)
˚
b (A)
27.273(3)
9.232(2)
23.055(2)
10.370(1)
13.403(2)
11.398(1)
19.7354(9)
12.1944(6)
9.774(1)
13.995(1)
10.533(3)
21.509(2)
˚
c (A)
a (ꢁ)
b (ꢁ)
c (ꢁ)
109.98(3)
2152(1)
111.6300(10)
2138.8(2)
116.907(4)
1727.8(3)
115.446(6)
4258.9(9)
˚
V (A)
4976.7(9)
1947.4(5)

S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
3021
(2H, d, J = 15.5), 7.06–7.09 (2H, m), 7.18–7.20 (4H,
m), 7.39–7.46 (3H, m), 7.59 (2H, d, J = 6.7), 7.84
(2H, dd, J = 7.9, 1.5). 13C NMR (CDCl3, 125.4
MHz): d 27.32 (C H3), 56.55 (CH2), 57.37 (C(CH3)3),
127.16, 127.23, 127.51, 128.85, 129.74, 139.01, 139.50,
149.13 (CCH2), 152.38 (CBi), 166.08 (CBi). Calc. for
C24H26BiN: C, 53.63; H, 4.88; N, 2.61. Found: C,
53.73; H, 4.79; N, 2.52%.
4.10. Preparation of [tBuN(CH2C6H4)2Bi{3,4-(CH2O2)-
C6H3}] (1h)
To a thf solution (100 ml) of 1b (5.01 g, 10.1 mmol)
was added 3,4-(CH2O2)C6H3MgBr in toluene/thf mix-
ture (1.0 M, 10.1 ml, 10.1 mmol) by syringe at ꢁ30
ꢁC. The mixture was stirred for 3 h with gradual warm-
ing to room temperature. Heptane (200 ml) was added
and the mixture was cooled to ꢁ78 ꢁC to settle insoluble
magnesium salts, which were removed by filtration. The
filtrate was concentrated to one third of the original vol-
ume and heptane (100 ml) was added; this operation was
repeated three times in order to remove thf and to settle
remaining magnesium salts. After the filtration, volatiles
were removed under vacuum. The residue was extracted
with 100 ml of CH2Cl2/hexane (1/4) to remove less solu-
ble bromide 1c, and the extract was concentrated under
vacuum. Recrystallization of the residual solid from
CH2Cl2/hexane at ꢁ25 ꢁC afforded colorless crystal of
1
1h (1.20 g, 24%); m.p. 172–173 ꢁC. H NMR (CDCl3,
499.1 MHz): d 1.21 (9H, s), 3.84 (2H, d, J = 15), 4.17
(2H, d, J = 15), 5.97 (2H, s), 6.94 (1H, d, J = 7.6),
7.09–7.13 (2H, m), 7.20 (4H, d, J = 4.0), 7.28–7.30
(2H, m), 7.62 (2H, d, J = 7.3). 13C NMR (CDCl3,
125.4 MHz): d 27.30 (C H3), 56.55 (CH2N), 57.37
(C(CH3)3), 100.17 (CH2O), 110.52, 119.04, 127.25,
127.48, 128.88, 132.61, 138.93, 146.97 (COCH2),
149.14 (CCH2N), 149.98 (COCH2), 152.61 (CBi),
158.01 (CBi). Calc. for C25H26BiNO2: C, 51.64; H,
4.51; N, 2.41. Found: C, 51.86; H, 4.42; N, 2.32%.
4.11. Preparation of [tBuN(CH2C6H4)2Bi{2,4,6-
(MeO)3C6H2}] (1i)
To a thf solution (50 ml) of 2,4,6-(MeO)3C6H2Li
(2.82 g, 16.2 mmol) was added 1b (4.01 g, 8.11 mmol)
in one portion at ꢁ78 ꢁC. The mixture was stirred at
the same temperature for 1 h, then gradually warmed
to 0 ꢁC over 4 h with stirring and then kept at room tem-
perature overnight. After the addition of hexane (90 ml),
insoluble materials were filtered off and the filtrate was
washed with water, dried over anhydrous Na2SO4, and
concentrated under vacuum. Then the residue was sub-
jected to bulb-to-bulb distillation to remove 1,3,5-
(MeO)3C6H3 under high vacuum and left 4.02 g of a
crude mixture consisted of 1i, 1b and 1,3,5-(MeO)3C6H3
(83/13/4 by weight; at this stage, calculated yield of 1i

3022
S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
was 66%). Pure 1i (0.85 g, 17%) was obtained by
repeated fractional solvent extraction and fractional
precipitation (hexane, hexane/EtOAc mixture, and
CH2Cl2 were used); m.p. 160–163 ꢁC. 1H NMR (CDCl3,
499.1 MHz): d 1.20 (9H, s), 3.46 (6H, s), 3.87 (2H, d,
J = 15.5), 3.89 (3H, s), 4.17 (2H, d, J = 15.5), 6.29
(2H, s), 7.00 (2H, dt, J = 1.5, 7), 7.12–7.18 (4H, m),
7.77 (2H, br d, J = 7.5). 13C NMR (CDCl3, 125.4
MHz): d 27.42 (CCH3), 55.21, 55.24, 55.78, 57.34,
90.92, 126.44, 126.77, 128.01, 140.05, 148.93, 162.77,
165.48. Calc. for C27H32BiNO3: C, 51.68; H, 5.14; N,
2.23. Found: C, 51.82; H, 5.05; N, 2.05%.
57.94 (C(CH3)3), 111.14 CC6H5), 112.31 CCC6H5),
125.39, 127.14, 127.27, 127.63, 128.11, 129.92, 131.84,
140.62, 148.75 (CCH2), 154.46 (CBi). Calc. for
C26H26BiN: C, 55.62; H, 4.67; N, 2.49. Found: C,
55.71; H, 4.67; N, 2.41%.
4.14. Preparation of [tBuN(CH2C6H4)2BiCH3] (1l)
To an Et2O solution (100 ml) of 1b (4.0 g, 8.1
mmol) was added an Et2O solution of MeLi (1.4 M,
6.0 ml, 8.4 mmol) via a syringe at ꢁ78 ꢁC. Then the
mixture was allowed to warm to room temperature
by removing the cooling bath and stirred for 21 h.
The mixture was filtered through Celite under nitrogen
and the filtrate was concentrated under vacuum. The
residue was dissolved in a CH2Cl2/hexane mixture
(1/2, 30 ml) and the solution was filtered through Cel-
ite under nitrogen. The filtrate was concentrated to ca.
10 ml under vacuum to give 1l as colorless crystals,
which were filtered, washed with hexane and dried un-
4.12. Preparation of [tBuN(CH2C6H4)2BiCMeCH2]
(1j)
To an Et2O solution (50 ml) of 1b (4.96 g, 10.0 mmol)
was added a thf solution of 2-propenylmagnesium bro-
mide (0.50 M, 25 ml, 12.5 mmol) at ꢁ70 ꢁC. After 10
min, the cooling bath was removed and the mixture
was stirred for 2 h. The solvent was evaporated and
the residue was extracted with a mixture of CH2Cl2/hex-
ane (1/1, 30 ml). After removal of the solvent under vac-
uum, the residue was purified by alumina column
chromatography (hexane) to afford 1j (3.7 g, 74%) as a
light yellow solid; m.p. 88.5–90.0 ꢁC. 1H NMR (CDCl3,
499.1 MHz): d 1.15 (9H, s), 2.59 (3H, t, J = 1.5), 3.79
(2H, d, J = 15.4), 4.10 (2H, d, J = 15.4), 5.62 (1H, m),
6.75 (1H, m), 7.18–7.23 (6H, m), 7.87–7.90 (2H, m).
13C NMR (CDCl3, 125.4 MHz): d 27.36 (C(CH3)3),
27.75 (CH2‚CCH3), 56.69 (NCH2), 57.21 (C(CH3)3),
127.20, 127.75, 128.24 (CH2‚C), 128.65, 138.54,
149.08 (CCH2N), 152.26 (CBi), 172.98 (CBi). Calc. for
C21H26BiN: C, 50.30; H, 5.23; N, 2.79. Found: C,
50.57; H, 5.20; N, 2.69%.
1
der vacuum. 3.4 g (89%); m.p. 119–121 ꢁC. H NMR
(CDCl3, 499.1 MHz): d 1.18 (9H, s), 1.20 (3H, s), 3.75
(2H, d, J = 15.5), 4.13 (2H, d, J = 15.5), 7.10 (2H, dd,
J = 1.0, 7.5), 7.17 (2H, dt, J = 1.0, 7.5), 7.21 (2H, dt,
J = 1.0, 7.5), 7.85 (2H, dd, J = 1.0, 7.5). 13C NMR
(CDCl3, 125.4 MHz):
d 15.60 (Bi–CH3), 27.17
(C(CH3)3), 56.19 (CH2), 57.08 (C(CH3)3), 127.10,
127.15, 128.51, 136.48, 144.12, 148.05. Calc. for
C19H24BiN: C, 48.00; H, 5.09; N, 2.95. Found: C,
48.14; H, 4.96; N, 2.77%.
4.15. Preparation of [tBuN(CH2C6H4)2BiSPh] (1m)
Chloride 1b (2.97 g, 5.99 mmol) was added into a
solution of PhSLi (prepared from PhSH (0.67 ml, 6.6
mmol) and nBuLi (1.55 M hexane solution, 4.3 ml,
6.6 mmol) in thf (30 ml)). Immediately, the color of
the solution turned to orange. After the mixutre was
refluxed for 5 h, the solvent was removed under
vacuum. The residue was dissolved in CH2Cl2, filtered
through a filter paper, and the filtrate was evaporated.
The residue was passed through alumina (CH2Cl2/hex-
ane, 1/5) and the eluate was partially concentrated un-
der vacuum. The addition of hexane to the solution
gave 1m (2.2 g, 64%) as white crystals; m.p. 167–169
ꢁC. 1H NMR (CDCl3, 499.1 MHz): d 1.25 (9H, s),
3.95 (2H, d, J = 15.2), 4.34 (2H, d, J = 15.2), 7.07
(2H, tt, J = 7.3, 1.4), 7.17–7.21 (2H, m), 7.29–7.34
(4H, m), 7.40–7.43 (2H, m), 7.54–7.56 (2H, m), 8.81–
8.83 (2H, m). 13C NMR (CDCl3, 125.4 MHz): d
27.50 (CH3), 58.38 (CH2), 58.88 (C(CH3)3), 124.50,
127.58, 127.86, 128.37, 130.39, 134.67, 139.32, 139.96
(CS), 150.08 (CCH2), 161.84 (CBi). Calc. for
C18H21BiClN: C, 50.61; H, 4.60; N, 2.46. Found: C,
50.74; H, 4.45; N, 2.36%.
4.13. Preparation of [tBuN(CH2C6H4)2BiCCPh] (1k)
An Et2O/hexane solution of PhC„CLi was prepared
by the addition of nBuLi (1.56 M hexane solution, 13 ml,
20 mmol) to an Et2O (24 ml) solution of PhC„CH (2.2
ml, 20 mmol) at ꢁ15 ꢁC and gradual warming to room
temperature. The PhC„CLi solution (20 ml, ca. 10
mmol) was added to an Et2O (150 ml) solution of 1b
(5.00 g, 10.1 mmol) at ꢁ78 ꢁC. Then the mixture was
warmed to room temperature over 10 h with stirring.
After removal of the solvent under vacuum, the residue
was extracted with a CH2Cl2/hexane mixture (1/1, 100
ml). The solution was filtered through Celite and evapo-
rated to leave a crude solid product, which was recrys-
tallized from a CH2Cl2/hexane mixture to give 1k (4.90
1
g, 87%) as colorless crystals; m.p. 147.5–149.0 ꢁC. H
NMR (CDCl3, 499.1 MHz): d 1.24 (9H, s), 3.83 (2H,
d, J = 15.2), 4.25 (2H, d, J = 15.2), 7.23–7.34 (9H, m),
7.57–7.59 (2H, m), 8.81–8.83 (2H, m). 13C NMR
(CDCl3, 125.4 MHz): d 27.27 (CH3), 56.91 (CH2),

S. Shimada et al. / Journal of Organometallic Chemistry 689 (2004) 3012–3023
3023
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