Synthesis and structures of hypervalent organoantimony and organobismuth chlorides containing asymmetric C,E,C-chelating (E = O, S) ligands

Article abstract of DOI:10.1039/c3dt50922b

Two asymmetric tridentate C,E,C-chelating ligand precursors, 1-Br-2-[(2′-BrC₆H₄CH₂E)CH ₂]C₁₀H₆ (E = O (1), E = S (2), were prepared in good yield. Lithiation of the two precursors was achieved by a reaction with n-BuLi, and was followed by treatment with SbCl₃ or BiCl₃ in a 1:1 molar ratio to give four air-stable hypervalent organoantimony and organobismuth chlorides with an asymmetric C,E,C-chelating ligand (E = O, S), i.e. (C₆H₄CH₂OCH₂C ₁₀H₆)SbCl (3), (C₆H₄CH ₂SCH₂C₁₀H₆)SbCl (4), (C ₆H₄CH₂OCH₂C₁₀H ₆)BiCl (5) and (C₆H₄CH₂SCH ₂C₁₀H₆)BiCl (6). These compounds were characterized by NMR spectroscopy, elemental analysis and melting point determination. X-ray structure analysis of compounds 3-6 revealed that the donor atoms (O, S) are strongly coordinated to the metal atoms (Sb, Bi). Compounds 3-6 exhibit chirality and crystallize as racemic mixtures. The Royal Society of Chemistry 2013.

Full text of DOI:10.1039/c3dt50922b

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Synthesis and structures of hypervalent
organoantimony and organobismuth chlorides
containing asymmetric C,E,C-chelating (E = O, S)
ligands†
Cite this: Dalton Trans., 2013, 42, 9476
Nianyuan Tan,‡a,b Yi Chen,‡a,c Shuang-Feng Yin,*a Renhua Qiu,a Yongbo Zhoua and
C. T. Aua,d
Two asymmetric tridentate C,E,C-chelating ligand precursors, 1-Br-2-[(2’-BrC6H4CH2E)CH2]C10H6 (E = O
(1), E = S (2), were prepared in good yield. Lithiation of the two precursors was achieved by a reaction
with n-BuLi, and was followed by treatment with SbCl3 or BiCl3 in a 1 : 1 molar ratio to give four air-
stable hypervalent organoantimony and organobismuth chlorides with an asymmetric C,E,C-chelating
ligand (E = O, S), i.e. (C6H4CH2OCH2C10H6)SbCl (3), (C6H4CH2SCH2C10H6)SbCl (4), (C6H4CH2OCH2C10H6)BiCl
(5) and (C6H4CH2SCH2C10H6)BiCl (6). These compounds were characterized by NMR spectroscopy,
elemental analysis and melting point determination. X-ray structure analysis of compounds 3–6 revealed
that the donor atoms (O, S) are strongly coordinated to the metal atoms (Sb, Bi). Compounds 3–6 exhibit
chirality and crystallize as racemic mixtures.
Received 8th April 2013,
Accepted 9th April 2013
DOI: 10.1039/c3dt50922b
www.rsc.org/dalton
to stabilize hypervalent organoantimony and organobismuth
halides,4 cations,5 chalcogen derivatives6 or compounds con-
Introduction
In recent years, hypervalent organoantimony and organobis- taining metal–metal bonds.4d,6a,7 Among these compounds,
muth compounds bearing intramolecular E→M (E = N, O, S; those with intramolecular N→Sb or N→Bi interactions are well
M = Sb, Bi) coordinations have attracted much attention due to studied while those with E→M (E = O, S; M = Sb, Bi) intramole-
their intriguing chemistry, structure and applications in areas cular coordinations are somewhat less reported.2,3 To the best
such as medicine, catalysis, and organic synthesis.1–3 The of our knowledge, only the crystal structures of two com-
majority of these compounds contain bidentate or tridentate pounds with S→Sb intramolecular coordinations, viz. CpFe-
aryl ligands with one or two pendant coordinating groups, i.e. [2-(RCH2)C5H3]SbPh2 [R = SCH2(furan)-2-yl]3,8 and [S(CH2-
9
the so-called C,E or E,C,E and C,E,C-chelating ligands (E = 2-C6H4SbMe3)2]I2 have been determined by X-ray diffraction
N, O, S). For example, the 2-[Me2NCH2]C6H4, 2,6- analysis.
(Me2NCH2)2C6H3, 2,6-(ROCH2)2C6H3 (R
=
Me, t-Bu) and
In contrast to hypervalent organoantimony and organobis-
E(CH2C6H4)2 (E = RN, O, S) moieties have often been applied muth compounds containing symmetric tridentate E,C,E-
ligands or C,E,C-ligands (E = N, O, S), the counterparts with
asymmetric analogous ligands have been only scantily
reported. Recently, a number of organoantimony and organo-
bismuth compounds with asymmetric N,C,O-ligands, i.e.
LSbCl2, LBiCl2 (L = [2-(Me2NCH2)-6-(ROCH2)C6H3], R = Me,10
t-Bu11) and [LMCl]+X− (L = [2-(Me2NCH2)-6-(t-BuOCH2)C6H3],11
M = Sb, X = [CB11H12]−; M = Bi, X = CF3SO3−, [CB11H12]−) as
well as (LME)2 (L = [2-(Me2NCH2-6-(MeOCH2)C6H3],12 M = Sb,
E = S or Se; M = Bi, E = S) were synthesized and characterized.
So far there are no organoantimony and organobismuth com-
pounds with asymmetric C,E,C-chelating (E = N, O, S) ligands
reported.
aState Key Laboratory of Chemo/Biosensing and Chemometrics, College of Chemistry
and Chemical Engineering, Hunan University, Changsha 410082, PR China.
E-mail: sf_yin@hnu.edu.cn; Fax: +86-731-88821171; Tel: +86-731-88821171
bCollege of Chemistry and Chemical Engineering, Hunan Institute of Engineering,
Xiangtan 411104, PR China
cSchool of Basic Medicine, Hunan University of Chinese Medicine, Changsha 410208,
PR China
dDepartment of Chemistry, Hong Kong Baptist University, Kowloon Tong, Hong Kong,
PR China
†Electronic supplementary information (ESI) available: 1H and 13C NMR of 1–6
(Fig. S1–S12) and crystallographic details (Tables S1–S4). CCDC numbers 773956
(3), 827987 (4), 909196 (5) and 909197 (6). For ESI and crystallographic data in
CIF or other electronic format see DOI: 10.1039/c3dt50922b
‡These authors contributed equally.
As part of our work on hypervalent organoantimony and
organobismuth compounds with C,E,C-chelating (E = N, O, S)
9476 | Dalton Trans., 2013, 42, 9476–9481
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ligands, we report herein the synthesis and structures of four
hypervalent organoantimony and organobismuth chlorides
containing asymmetric C,E,C-chelating (E = O, S) ligands.
Results and discussion
Two asymmetric tridentate C,E,C-ligand (E = O, S) precursors,
viz. 1-bromo-2-[(2-bromobenzyloxy)methyl]naphthalene (1) and
(2-bromobenzyl)[(1-bromonaphthalen-2-yl)methyl]sulfane (2),
were prepared by nucleophilic substitution of 1-bromo-2-bro-
momethylnaphthalene13 with the nucleophilic reagent gener-
ated by reacting (2-bromophenyl)methanol or (2-bromophenyl)-
methanethiol with NaH, respectively (Scheme 1). Both com-
pounds were isolated as colorless transparent solids after
recrystallization from CH2Cl2–hexane (92% for 1, 87% for 2).
Compounds 1 and 2 were lithiated with n-BuLi at −30 °C, and
the resulting dilithio compounds reacted with SbCl3 or BiCl3
in a 1 : 1 molar ratio to produce the corresponding chlorides,
i.e. 14-chloro-7,14-dihydro-5H-benzo[c]naphtho[1,2-f][1,5]oxas-
tibocine (3), 14-chloro-7,14-dihydro-5H-benzo[c]naphtho[1,2-f]-
Fig. 1 A thermal ellipsoid plot of the (CSb)-3 isomer (50% probability level).
[1,5]thiastibocine (4),
naphtho[1,2-f][1,5]oxabismocine (5) and 14-chloro-7,14-
dihydro-5H-benzo[c]naphtho[1,2-f][1,5]thiabismocine (6)
14-chloro-7,14-dihydro-5H-benzo[c]-
(Scheme 1). The crystals of compounds 3 and 4 are colorless
and transparent while those of compounds 5 and 6 are yellow.
Compounds 3–5 are well soluble in chlorinated solvents
(CH2Cl2, CHCl3) while compound 6 is only slightly soluble in
chlorinated solvents (CH2Cl2, CHCl3). Compounds 3–6 are air-
stable and thermally stable up to 200 °C. The NMR and
elemental analytical data of compounds 1–6 are consistent
with their formulas.
Fig. 2 A thermal ellipsoid plot of the (ASb)-4 isomer (50% probability level).
The molecular structures of chlorides 3–6 determined by
X-ray diffraction analysis of the single crystals obtained by slow
diffusion of n-hexane into CH2Cl2 solutions are depicted in
Fig. 1–4. Selected bond distances and angles are given in
Table 1.
Fig. 3 A thermal ellipsoid plot of the (CBi)-5 isomer (50% probability level).
A common feature of organoantimony and organobismuth
chlorides 3–6 is that the metal centre (Sb, Bi) is strongly co-
ordinated with the donor O or S atom of the asymmetric triden-
tate C,E,C-ligand (E = O, S). The intramolecular E→Sb or E→Bi
interactions result in the formation of “chelate induced-M-chiral”
(M = Sb, Bi) compounds.3,14 For compounds 3–6, chirality
(induced at Sb or Bi) can be described in terms of the CM and
Fig. 4 A thermal ellipsoid plot of the (CBi)-6 isomer (50% probability level).
AM isomers having pseudo-trigonal bipyramidal cores.3,14 It is
apparent that compounds 3–6 crystallize as racemates.
One can see that the coordination polyhedron around the
centre metal (Sb, Bi) of compounds 3–6 can be best described
Scheme 1 Synthesis of compounds 1–6.
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(E = N, O) [range of Sb–S bond lengths: 2.4109(15)–2.677(2)
Å],6a,e,g and is significantly shorter than the Sb(1)–S(1) distance
[3.555(2) Å] in [S(CH2-2-C6H4SbMe3)2]I2.9 The Bi(1)–S(1) bond
length [2.819(2) Å] of 6 is slightly shorter than that of
S(CH2C6H4)2BiCl [2.845(4) Å],4i suggesting that the S→Bi
coordination of the former is slightly stronger than that of the
latter, and longer than that of the organobismuth cations
with a 5,6,7,12-tetrahydrodibenz[c,f][1,5]thiobismocine frame-
work, i.e. [S(CH2C6H4)2Bi(OH2)]+[ClO4]−,5d [S(CH2C6H4)2Bi-
Table 1 Selected bond lengths [Å] and angles [°] of 3–6
3
Sb(1)–C(1)
Sb(1)–C(18)
Sb(1)–O(1)
Sb(1)–Cl(1)
O(1)–C(7)
O(1)–C(8)
4
2.176(4)
2.165(3)
2.425(2)
2.4793(10)
1.433(4)
1.437(4)
C(1)–Sb(1)–C(18)
C(1)–Sb(1)–O(1)
C(18)–Sb(1)–O(1)
C(1)–Sb(1)–Cl(1)
C(18)–Sb(1)–Cl(1)
O(1)–Sb(1)–Cl(1)
101.55(13)
72.74(11)
73.77(11)
88.81(10)
98.12(10)
157.43(7)
Sb(1)–C(1)
Sb(1)–C(18)
Sb(1)–S(1)
Sb(1)–Cl(1)
S(1)–C(7)
S(1)–C(8)
5
Bi(1)–C(1)
Bi(1)–C(18)
Bi(1)–O(1)
Bi(1)–Cl(1)
O(1)–C(7)
O(1)–C(8)
6
2.186(3)
2.184(3)
2.7515(7)
2.5260(7)
1.799(3)
1.815(3)
C(1)–Sb(1)–C(18)
C(1)–Sb(1)–S(1)
C(18)–Sb(1)–S(1)
C(1)–Sb(1)–Cl(1)
C(18)–Sb(1)–Cl(1)
S(1)–Sb(1)–Cl(1)
106.01(10)
76.19(7)
73.24(7)
89.78(7)
89.55(7)
153.39(2)
(OH2)]+[BF4],5f
[S(CH2C6H4)2Bi(OH2)]+[OSO2C4F9]−5j
and
[S(CH2C6H4)2Bi(OH2)]+[OSO2C8F17]−5e [range of Bi–S bond
lengths: 2.693(3)–2.713(1) Å], indicating that the S→Bi coordi-
nation in 6 is weaker than that of the organobismuth cations
containing a symmetric tridentate C,S,C-ligand. A similar
value for the Bi–S bond distance was found in 4,8-di-tert-butyl-
6-iodo-2,10-dimethyldibenzo[d,g][1,3,6,2]dioxathiabismocine
[Bi(1)–S(1) 2.8165(15) Å].16 The Sb–Cl and Bi–Cl bond distances
in 4 [2.5260(7) Å] and 6 [2.655(2) Å] containing S→M (M = Sb,
2.289(4)
2.270(4)
2.548(2)
2.5803(10)
1.446(4)
1.460(6)
C(1)–Bi(1)–C(18)
C(1)– Bi(1)–O(1)
C(18)–Bi(1)–O(1)
C(1)–Bi(1)–Cl(1)
C(18)–Bi(1)–Cl(1)
O(1)–Bi(1)–Cl(1)
100.59(13)
70.10(12)
71.35(12)
88.77(10)
95.87(9)
152.02(13)
Bi) coordinations are slightly longer than those in
3
Bi(1)–C(1)
Bi(1)–C(18)
Bi(1)–S(1)
Bi(1)–Cl(1)
S(1)–C(7)
S(1)–C(8)
2.296(7)
2.292(7)
2.819(2)
2.655(2)
1.788(9)
1.817(8)
C(1)–Bi(1)–C(18)
C(1)– Bi(1)–S(1)
C(18)–Bi(1)–S(1)
C(1)–Bi(1)–Cl(1)
C(18)–Bi(1)–Cl(1)
S(1)–Bi(1)–Cl(1)
100.3(3)
74.0(2)
74.3(2)
88.7(2)
92.1(2)
155.32(7)
[2.4793(10) Å] and 5 [2.5803(10) Å] containing O→M (M = Sb,
Bi) interactions. The phenomenon is ascribable to the stronger
electron-donating ability of the S atom compared with that of
the O atom, which is consistent with the Lewis acidity of the Sb
or Bi centre associated with the Sb–X or Bi–X σ* orbitals.4b,c,d
The 1H NMR spectra for compounds 1 and 2 in CDCl3 at
as a strongly distorted pseudo-trigonal bipyramid (hypervalent room temperature contain two singlet signals (1, δ 4.73, 4.95;
10-Sb-4 or 10-Bi-4 species15). The O(1) or S(1) and Cl(1) atoms 2, δ 3.84, 4.09 ppm) ascribable to the two methylene units,
are located at the apical positions, and the C(1)and C(18) which is consistent with their non-equivalence. For com-
atoms at the equatorial positions along with a lone pair of Sb pounds 3–6 the signals for the two CH2 groups exhibit two AB
or Bi. Due to the constrains imposed by the intramolecular systems, i.e. two pairs of doublet signals as in the case of 4
E→M (E = O, S; M = Sb, Bi) coordinations, the E–M–Cl angles (Fig. S7†) and 6 (Fig. S11†) as a result of intramolecular E→M
in compounds 3–6 [3, O(1)–Sb(1)–Cl(1): 157.43(7)°; 4, S(1)– (E = O, S; M = Sb, Bi) coordinations. In compound 5, the two
Sb(1)–Cl(1): 153.39(2)°; 5, O(1)–Bi(1)–Cl(1): 152.02(13)°; 6, S(1)– doublet signals of the CH2 protons at a lower field partially
Bi(1)–Cl(1): 155.32(7)°] significantly deviate from the ideal case overlap and look like a triplet (Fig. S9†). On the other hand, by
of 180°. Furthermore, compared with the C–M–C angles of chance the two signals from one of the CH2 groups of 3
organoantimony and organobismuth chlorides containing showed an identical chemical shift and appeared as a singlet
symmetric tridentate C,E,C-ligands (E = N, O, S), [such as CyN- with 2H integration (Fig. S5†), while the signals from the other
(CH2C6H4)2SbCl: 92.95(10)°,4l t-BuN(CH2C6H4)2BiCl: 93.6(1)°,4e CH2 group appeared as the usual doublet pair.
PhN(CH2C6H4)2BiCl:
92.90(2)°,4i
CyN(CH2C6H4)2BiCl:
96.72(19)°4i and S(CH2C6H4)2BiCl: 98.90(5)°4i] the C–M–C
angles of chlorides 3–6 are wider, [C(1)–Sb(1)–C(18):
101.55(13)° for 3 and 106.01(10)° for 4; C(1)–Bi(1)–C(18):
100.59(13)° for 5 and 100.3(3)° for 6], which is plausibly a
result of steric hindrance induced by the naphthyl group.
Conclusions
In summary, two asymmetric tridentate C,E,C-chelating (E = O,
The Sb(1)–O(1) distance [2.425(2) Å] of 3 is shorter than that S) ligand precursors 1, 2 and four hypervalent organoantimony
(2.626 Å) of 12-phenylethynyl-5H-7,12-dihydrodibenz[c,f][1,5] and organobismuth chlorides 3–6 containing an asymmetric
oxastibocine4g with
a symmetric tridentate C,O,C-ligand. C,E,C-chelating ligand (E = O, S), i.e. (C6H4CH2OCH2C10H6)-
However, the Bi(1)–O(1) distance [2.548(2) Å] of 5 is longer SbCl (3), (C6H4CH2SCH2C10H6)SbCl (4), (C6H4CH2OCH2C10H6)-
than that [2.417(7) Å] of organobismuth triflate BiCl (5) and (C6H4CH2SCH2C10H6)BiCl (6), were synthesized
[O(CH2C6H4)2Bi(OH2)]+[OSO2CF3]−5i with a 5,6,7,12-tetrahydro- and characterized. To the best of our knowledge, compounds
dibenzo[c,f][1,5]oxabismocine framework, suggesting that the 3–6 are the first examples of Sb and Bi (heavy group 15
O→Bi coordination in 5 is weaker than that in the organobis- elements) compounds bearing an asymmetric tridentate C,E,
muth cation containing a symmetric tridentate C,O,C-ligand. C-ligand. X-ray structure analysis of 3–6 revealed that the
The Sb(1)–S(1) distance [2.7515(7) Å] in 4 is slightly shorter donor atoms (O, S) are strongly coordinated to the metal
than the distances of the covalent single Sb–S bonds in organo- atoms (Sb, Bi). The four compounds exhibit chirality and crys-
antimony sulfides with intramolecular E→Sb interactions tallize as racemic mixtures.
9478 | Dalton Trans., 2013, 42, 9476–9481
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1
51.14; H, 3.32. H NMR (400 MHz, CDCl3, TMS): δ = 3.84 (2H,
s), 4.09 (2H, s), 7.09 (1H, t, J = 7.6 Hz), 7.23 (1H, t, J = 8.4 Hz),
7.35 (1H, d, J = 7.6 Hz), 7.49–7.56 (3H, m), 7.59 (1H, t, J =
Experimental
General
All manipulations of air-sensitive materials were performed in 8.4 Hz), 7.74 (1H, d, J = 8.4 Hz), 7.79 (1H, d, J = 8.0 Hz), 8.30
a glove box filled with argon or under a nitrogen atmosphere (1H, d, J = 8.8 Hz); 13C NMR (CDCl3, 100 MHz, TMS): δ = 36.50,
using the standard Schlenk techniques. The chemicals were 37.49, 124.40, 124.63, 126.42, 127.43, 127.46, 127.51, 127.75,
purchased from Aldrich as well as some other chemical provi- 127.82, 128.05, 128.65, 130.74, 132.42, 133.03, 133.57, 135.49,
ders. They were used as received unless otherwise indicated. 137.21.
All solvents were dried by standard procedures and distilled
Synthesis of (C6H4CH2OCH2C10H6)SbCl (3). Compound 1
prior to use. 1-Bromo-2-bromomethylnaphthalene was pre- (4.06 g, 10.0 mmol) was dissolved in Et2O (100 mL), and
pared according to literature procedures.13 The NMR spectra 8.8 mL (22 mmol, 2.5 M in hexane) of n-butyllithium was
were recorded at room temperature using a Bruker Avance III added dropwise to the solution at −30 °C. The mixture was
400 spectrometer (Germany). Chemical shifts given in ppm are gradually warmed to room temperature over a period of 3 h,
1
referenced to tetramethylsilane for H NMR spectra (0.0 ppm) and then a solution of SbCl3 (2.28 g, 10 mmol) in Et2O
and to the solvent signal (CDCl3) for 13C NMR spectra (100 mL) was added at −78 °C. The resulting mixture was
(77.0 ppm), and coupling constants were reported in hertz. gradually warmed to room temperature over a period of 12 h
Elemental analysis was performed using a VARIO EL III and then continuously stirred for 6 h at room temperature.
(Germany). The melting points of the compounds were deter- After the removal of Et2O under vacuum and toluene extrac-
mined using a XT-4 micro apparatus (Beijing Tech Instrument tion, the insoluble material was filtered out, and the organic
Co. Ltd) and are not corrected.
layer was washed with brine and dried over anhydrous MgSO4.
Synthesis of 1-Br-2-[(2′-BrC6H4CH2O)CH2]C10H6 (1). To a The solvent was removed under reduced pressure and the
suspension of NaH (1.50 g, 80% oil dispersion, 0.05 mol) in residue was recrystallized from CH2Cl2–hexane to give com-
THF (50 mL), (2-bromophenyl)methanol (7.48 g, 0.04 mol) was pound 3 in the form of colorless crystals. Yield: 1.05 g (26%).
added at 0 °C over 30 min, and the mixture was stirred for 2 h. Mp: 196–198 °C. Anal. calcd for C18H14SbClO (403.52): C,
Then,
a
solution of 1-bromo-2-bromomethylnaphthalene 53.58; H, 3.50; found: C, 53.56; H, 3.49. 1H NMR (400 MHz,
(12.0 g, 0.04 mol) in THF (80 mL) was added dropwise at 0 °C. CDCl3, TMS): δ = 4.87 (1H, d, J = 14 Hz), 5.04 (2H, s), 5.27(1H,
The reaction mixture was heated at reflux for 4 h. After d, J = 14 Hz), 7.12 (1H, d, J = 8.4 Hz), 7.28 (1H, d, J = 7.6 Hz),
cooling, the reaction mixture was diluted with Et2O (150 mL) 7.39 (1H, t, J = 7.2 Hz), 7.47–7.52 (2H, m), 7.60 (1H, t, J =
and quenched with water (50 mL). The organic layer was sepa- 8.0 Hz), 7.75 (1H, d, J = 8.4 Hz), 7.82 (1H, d, J = 8.0 Hz), 8.43
rated, washed with NH4Cl, and dried over anhydrous Na2SO4. (1H, d, J = 7.2 Hz), 8.97 (1H, d, J = 8.8 Hz); 13C NMR (CDCl3,
The solvent was removed under reduced pressure and the 100 MHz, TMS): δ = 73.74, 74.78, 121.81, 125.46, 125.92,
residue was recrystallized from CH2Cl2–hexane to give com- 125.99, 128.52, 129.14, 130.01, 130.04, 130.29, 134.11, 135.78,
pound 1 in the form of colorless crystals. Yield: 14.92 g (92%). 136.37, 137.21, 141.28, 141.89, 142.32.
Mp: 80–81 °C. Anal. calcd for C18H14Br2O (406.11): C, 53.23; H,
Synthesis of (C6H4CH2SCH2C10H6)SbCl (4). Compound 2
3.47; found: C, 53.14; H, 3.46. 1H NMR (400 MHz, CDCl3, (2.12 g, 5 mmol) was dissolved in Et2O (80 mL), and 4.4 mL
TMS): δ = 4.73 (2H, s), 4.95 (2H, s), 7.15 (1H, t, J = 8.0 Hz), 7.33 (11 mmol, 2.5 M in hexane) of n-butyllithium was added drop-
(1H, t, J = 7.6 Hz), 7.51(1H, t, J = 8.0 Hz), 7.54–7.60 (3H, m), wise to the solution at −30 °C. The mixture was gradually
7.69 (1H, d, J = 8.4 Hz), 7.81 (2H, d, J = 8.4 Hz), 8.30 (1H, d, J = warmed to room temperature over a period of 3 h, and then a
8.8 Hz); 13C NMR (CDCl3, 100 MHz, TMS): δ = 72.02, 72.75, solution of SbCl3 (1.14 g, 5 mmol) in Et2O (50 mL) was added
122.43, 122.66, 125.88, 126.44, 126.95, 127.37, 127.42, 127.73, at −78 °C. The resulting mixture was gradually warmed to
128.10, 128.98, 129.05, 132.06, 132.49, 133.93, 135.56, 137.36.
room temperature over a period of 12 h and then continuously
Synthesis of 1-Br-2-[(2′-BrC6H4CH2S)CH2]C10H6 (2). To a stirred for 6 h at room temperature. After removal of Et2O
suspension of NaH (1.20 g, 80% oil dispersion, 0.04 mol) in under vacuum and toluene extraction, the insoluble material
THF (40 mL), a solution of (2-bromophenyl)methanethiol was filtered out, and the organic layer was washed with brine
(6.09 g, 0.03 mol) in THF (15 mL) was added dropwise at 0 °C and dried over anhydrous MgSO4. The solvent was removed
over 30 min, and the mixture was stirred for 2 h. Then, a solu- under reduced pressure and the residue was recrystallized
tion of 1-bromo-2-(bromomethyl)naphthalene (9.0 g, 0.03 mol) from CH2Cl2–hexane to give compound 4 in the form of color-
in THF (60 mL) was added dropwise at 0 °C. The reaction less crystals. Yield: 0.46 g (22%). Mp: 210–212 °C. Anal. calcd
mixture was heated at reflux for 4 h. After cooling, the reaction for C18H14SbClS (419.58): C, 51.53; H, 3.36; found: C, 51.50; H,
mixture was diluted with Et2O (100 mL) and quenched with 3.34. 1H NMR (400 MHz, CDCl3, TMS): δ = 4.17 (1H, d, J =
water (40 mL). The organic layer was separated, washed with 14.4 Hz), 4.22(1H, d, J = 14.4 Hz), 4.33 (1H, d, J = 16.0 Hz), 4.38
brine, and dried over anhydrous MgSO4. The solvent was (1H, d, J = 16.0 Hz), 7.22 (1H, d, J = 8.0 Hz), 7.30 (1H, d, J =
removed under reduced pressure and the residue was recrystal- 7.6 Hz), 7.36 (2H, m), 7.48 (1H, t, J = 7.6 Hz), 7.60 (1H, t, J =
lized from CH2Cl2–hexane to give compound 2 in the form of 8.4 Hz), 7.72 (1H, d, J = 7.6 Hz), 7.79 (1H, d, J = 8.0 Hz), 8.70
colorless crystals. Yield: 11.02 g (87%). Mp: 86–88 °C. Anal. (1H, d, J = 7.2 Hz), 8.91 (1H, d, J = 8.4 Hz); 13C NMR (CDCl3,
calcd for C18H14Br2S (422.18): C, 51.21; H, 3.34; found: C, 100 MHz, TMS): δ = 39.17, 39.27, 125.43, 125.82, 126.03,
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128.25, 128.90, 129.30, 129.38, 130.01, 131.79, 133.43, 137.40, stirred for 6 h at room temperature. After removal of Et2O
137.92, 138.08, 139.76, 144.78, 147.73. under vacuum and toluene extraction, the insoluble material
Synthesis of (C6H4CH2OCH2C10H6)BiCl (5). Compound 1 was filtered out, and the organic layer was washed with brine
(4.06 g, 10.0 mmol) was dissolved in Et2O (60 mL), and 8.8 mL and dried over anhydrous MgSO4. The solvent was removed
(22 mmol, 2.5 M in hexane) of n-butyllithium was added drop- under reduced pressure and the residue was recrystallized
wise to the solution at −30 °C. The mixture was gradually from CH2Cl2–hexane to give compound 6 in the form of yellow
warmed to room temperature over a period of 3 h, and then a crystals. Yield: 0.38 g (19%). Mp: 247–249 °C. Anal. calcd for
solution of BiCl3 (3.17 g, 10 mmol) in Et2O (100 mL) was C18H14BiClS (506.80): C, 42.66; H, 2.78; found: C, 42.62; H,
added at −78 °C. The resulting mixture was gradually warmed 2.74. 1H NMR (400 MHz, CDCl3, TMS): δ = 4.22 (1H, d, J = 14.0
to room temperature over a period of 12 h and then continu- Hz), 4.27 (1H, d, J = 16.4 Hz), 4.67(1H, d, J = 15.6 Hz), 4.99 (1H,
ously stirred for 6 h at room temperature. After removal of d, J = 14 Hz), 7.48 (2H, t, J = 7.6 Hz), 7.55–7.65 (3H, m), 7.67
Et2O under vacuum and toluene extraction, the insoluble (1H, d, J = 7.6 Hz), 7.85 (1H, d, J = 8.4 Hz), 7.91 (1H, d, J =
material was filtered out, and the organic layer was washed 8.0 Hz), 9.02 (1H, d, J = 8.8 Hz), 9.25 (1H, d, J = 7.6 Hz); 13C
with brine and dried over anhydrous MgSO4. The solvent was NMR (CDCl3, 100 MHz, TMS): δ = 40.27, 41.74, 126.23, 126.73,
removed under reduced pressure and the residue was recrystal- 127.81, 128.31, 128.52, 128.96, 131.42, 131.78, 132.44, 134.62,
lized from CH2Cl2–hexane to give compound 5 in the form of 140.51, 141.12, 144.63, 150.82.
yellow crystals. Yield: 1.86 g (38%). Mp: 230–231 °C. Anal.
calcd for C18H14BiClO (490.74): C, 44.05; H, 2.88; found: C,
44.02; H, 2.8. 1H NMR (400 MHz, CDCl3, TMS): δ = 4.96 (1H, d,
X-ray crystallography
J = 14.0 Hz), 5.04 (1H, d, J = 13.2 Hz), 5.28 (2H, t, J = 16 Hz),
7.42 (1H, t, J = 7.6 Hz), 7.45–7.50 (2H, m), 7.57 (1H, d, J = 7.6
Hz), 7.61 (1H, d, J = 8.4 Hz), 7.69 (1H, t, J = 7.2 Hz), 7.81 (1H,
d, J = 8.4 Hz), 7.93 (1H, d, J = 8.0 Hz), 9.05 (2H, m); 13C NMR
(CDCl3, 100 MHz, TMS): δ = 76.13, 78.17, 124.82, 126.12,
126.26, 127.76, 128.29, 128.72, 129.03, 131.37, 132.99, 136.01,
139.03, 141.09, 141.47, 143.75, 145.75.
Synthesis of (C6H4CH2SCH2C10H6)BiCl (6). Compound 2
(1.69 g, 4 mmol) was dissolved in Et2O (100 mL), and 3.5 mL
(8.8 mmol, 2.5 M in hexane) of n-butyllithium was added drop-
wise to the solution at −30 °C. The mixture was gradually
warmed to room temperature over a period of 3 h, and then a
solution of BiCl3 (1.26 g, 4 mmol) in Et2O (50 mL) was added
at −78 °C. The resulting mixture was gradually warmed to
room temperature over a period of 12 h and then continuously
Given in Table 2 are the results of the crystal structure determi-
nation and refinement for compounds 3–6. X-ray single crystal
diffraction analysis was performed at the Shanghai Institute of
Organic Chemistry, Chinese Academy of Sciences using a
Bruker SMART APEX diffractometer. In all cases, the diffrac-
tion data were collected using graphite monochromated
Mo-Ka radiation (λ = 0.71073 Å). The collected frames were pro-
cessed with SAINT+17 software and an absorption correction
(SADABS)18 was applied to the collected reflections. The struc-
ture was solved by the Direct method (SHELXTL)19 in conjunc-
tion with standard difference Fourier techniques and
subsequently refined by full-matrix least-squares analyses
on F2. The hydrogen atoms were generated in their idealized
positions and all non-hydrogen atoms were refined
anisotropically.
Table 2 Crystallographic data for compounds 3–6
Compound
3
4
5
6
Empirical formula
M
C18H14SbClO
403.49
C18H14SbClS
419.55
C18H14BiClO
490.72
C18H14BiClS
506.78
T
293(2) K
Monoclinic
P2(1)/c
11.7504(10)
14.4272(12)
8.9688(8)
90.00
293(2) K
Monoclinic
P2(1)/n
11.4234(8)
11.2183(8)
13.3640(10)
90.00
133(2) K
Orthorhombic
Pna2(1)
20.5263(19)
15.8560(15)
4.5578(4)
90.00
293(2) K
Monoclinic
P2(1)/n
11.6940(12)
11.4596(12)
12.4340(13)
90.00
Crystal system
Space group
a/Å
b/Å
c/Å
α/°
β/°
93.251(2)
90.00
1518.0(2)
4
111.4280(10)
90.00
1594.2(2)
4
90.00
90.00
1483.4(2)
4
110.526(2)
90.00
1560.5(3)
4
γ/°
V/Å3
Z
No. of reflections collected
No. of unique reflections
Rint
8803
3307
0.1210
0.0411
9412
3129
0.0284
0.0257
10 320
3079
0.0266
0.0154
9015
3063
0.0852
0.0482
R1 [I > 2σ(I)]
R1 (all data)
0.0455
0.1079
0.1108
1.053
0.0284
0.0658
0.0672
1.052
0.0190
0.0354
0.0365
0.965
0.0552
0.1084
0.1118
1.029
wR2 [I > 2σ(I)]
wR2 (all data)
GOF on F2
9480 | Dalton Trans., 2013, 42, 9476–9481
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Acknowledgements
This work was supported by the Natural Science Foundation of
Hunan Province (10JJ1003), the Science Research Foundation
for Higher Universities of Hunan Province (10A092), the
Research-Based Learning and Innovation Experiment Project
for Undergraduates of Hunan Province (2011-483), the
National Natural Science Foundation of China (20973056,
21003040), and the Program for New Century Excellent Talents
in Universities (NCET-10-0371). CTA thanks HNU for an
adjunct professorship. S. F. Yin thanks Dr S. Shimada of AIST
(Japan) for helpful discussion.
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This journal is © The Royal Society of Chemistry 2013
Dalton Trans., 2013, 42, 9476–9481 | 9481