Syntheses and characterization of tributyltin(IV) carboxylates containing α-oxoketene cyclic dithioacetals

Article abstract of DOI:10.1081/SIM-120019995

Five aquatributyltin-2-(dialkylthio)methylene-3-oxo-5-aryl-4-pentenoates (3) were synthesized and characterized by IR spectra, ¹H NMR spectra, ¹³C NMR spectra and elemental analyses. The IR spectra of (3) show strong O - H stretching modes in the region of 3384-3455 cm^-1. In the ¹H NMR spectra of (3), signals due to the protons of an α-oxoketene dithioacetal segment shift upfield compared to those of free acids (2). This is indicative of the formation of the tin ester complexes. The structure of 4-O₂N-C₆H₄CH=CHCOC(C ₃H₄S₂)CO₂Sn(C ₄H₉)₃·(H₂O) (3d) was determined by X-ray diffraction and showed two molecules in an asymmetric unit cell. The tin(IV) is coordinated with three carbon atoms, an oxygen of carboxylate and an oxygen of water and forms a five-coordinate, distorted trigonal bipyramidal configuration. There is no intermolecular O - Sn coordination in (3d), but a molecule of water acts as one of the five ligands and coordinates directly to the tin atom. The tin - oxygen (water) bond distance in (3d) is discussed in relation to that in other aquatin(IV) complexes.

Full text of DOI:10.1081/SIM-120019995

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Syntheses and Characterization of Tributyltin(IV)
Carboxylates Containing α‐Oxoketene Cyclic
Dithioacetals
Fushun Liang a b , Jianxin Li a , Qun Liu a , Yan Xing b , Hengqing Jia b , Ninghai Hu b &
Yonghua Lin b
a Department of Chemistry , Northeast Normal University , Changchun, 130024, P.R. China
b State Key Laboratory of Polymer Physics and Chemistry , Changchun Institute of Applied
Chemistry , Chinese Academy of Sciences , Changchun, 130022, P.R. China
Published online: 15 Feb 2007.
To cite this article: Fushun Liang , Jianxin Li , Qun Liu , Yan Xing , Hengqing Jia , Ninghai Hu & Yonghua Lin (2003) Syntheses
and Characterization of Tributyltin(IV) Carboxylates Containing α‐Oxoketene Cyclic Dithioacetals, Synthesis and Reactivity in
Inorganic and Metal-Organic Chemistry, 33:3, 411-422, DOI: 10.1081/SIM-120019995
To link to this article: http://dx.doi.org/10.1081/SIM-120019995
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 3, pp. 411–422, 2003
Syntheses and Characterization of Tributyltin(IV)
Carboxylates Containing -Oxoketene
Cyclic Dithioacetals
2
Fushun Liang,1,2 Jianxin Li,1 Qun Liu,1, Yan Xing,
*
Hengqing Jia,2 Ninghai Hu,2 and Yonghua Lin2
1Department of Chemistry, Northeast Normal University
Changchun, P.R. China
2State Key Laboratory of Polymer Physics and Chemistry, Changchun
Institute of Applied Chemistry, Chinese Academy of Sciences,
Changchun, P.R. China
ABSTRACT
Five aquatributyltin-2-(dialkylthio)methylene-3-oxo-5-aryl-4-penteno-
ates (3) were synthesized and characterized by IR spectra, 1H NMR
spectra, 13C NMR spectra and elemental analyses. The IR spectra of (3)
show strong O—H stretching modes in the region of 3384–3455 cm–1. In
the 1H NMR spectra of (3), signals due to the protons of an a-oxoketene
dithioacetal segment shift upfield compared to those of free acids (2).
This is indicative of the formation of the tin ester complexes. The
*
Correspondence: Qun Liu, Department of Chemistry, Northeast Normal University,
Changchun 130024, P.R. China; E-mail: liuqun@nenu.edu.cn.
411
DOI: 10.1081/SIM-120019995
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

412
Liang et al.
structure of 4-O2N-C6H4CH=CHCOC(C3H4S2)CO2Sn(C4H9)3ꢀ(H2O)
(3d) was determined by X-ray diffraction and showed two molecules in
an asymmetric unit cell. The tin(IV) is coordinated with three carbon
atoms, an oxygen of carboxylate and an oxygen of water and forms a five-
coordinate, distorted trigonal bipyramidal configuration. There is no
intermolecular O—Sn coordination in (3d), but a molecule of water acts
as one of the five ligands and coordinates directly to the tin atom. The
tin oxygen (water) bond distance in (3d) is discussed in relation to that
in other aquatin(IV) complexes.
Key Words: Tributyltin (IV) carboxylates; a-Oxoketene cyclic
dithiocetals; Coordinating water; Structure.
INTRODUCTION
Organotin compounds have been extensively studied because of their
biological activities. In general, the fungicidal and antibacterial properties
of organotins in vitro have indicated that the order of activity is related to
the number of R groups attached to a tin atom. The order of activity has
been oberved to be: RSnX3 <R2SnX2 < R3SnX. The nature of the X group
has relatively little influence on the fungicidal activity of an organotin
compound.[1] However, studies have continued on the structures of various
triorganotin com-pounds, especially containing X groups which themselves
have some biological activities.[2–5] a-Oxoketene dithioacetals and related
compounds are versatile synthons in organic synthesis,[6–8] and then some
of them have been found to possess strong biological activities. In order to
study the relationship between structures and activities, we have prepared
herein five new tributyltin(IV) carboxylates containing an a-oxoketene
cyclic dithioacetal moiety.
In organotin compounds, R3SnO2CR’, the coordination environment of
the tin atom is normally determined by its spacial factors (volume) of the
substitute groups R and R’ and the electronic factors of R’.[9–11] Thus, the
study on the structure of triorganotin carboxylates is mainly embodied on
the alternation of R and R’ groups. In addition to the study of their
biological activities, we are also interested in the nature of the bond and
bond-structure in these compounds. In the present paper, the preparation
and characterization of 2-(1,2-ethylenedithio)methylene-3-oxo-5-aryl-4-pen-
tenoic acids (2a)–(2e) and the corresponding tin esters, that is, aqua-
tributyltin(IV)-2-(dialkylthio)methylene-3-oxo-5-aryl-4-pentenoates (3a)–
(3e) are described.

Tributyltin(IV) Carboxylates
413
EXPERIMENTAL
Materials and Methods
All operations were carried out under moisture-free conditions. All sol-
1
vents were dried by standard methods. H NMR spectra were recorded on a
Bruker Ac-80 spectrometer operating at 80 MHz and 13C NMR spectra were
recorded on a Varian XL-400 spectrometer operating at 100 MHz with TMS
as internal reference and chloroform-d as solvent. IR spectra were recorded
on a BIDF TS-135 FT-IR spectrophotometer with KBr pellets. Elemental
analyses were taken with a Bio-Rad Co. elemental analytical instrument.
Acyl (Alkoxycarbonyl)ketene Dithioacetal (1)
To a well-stirred suspension of ethyl acetoacetate (13.00 g, 0.10 mol)
and anhydrous potassium carbonate (42.00 g, 0.30 mol) in N,N-dime-
thylformamide (50 mL) was added carbon disulfide (9.00 mL, 0.15 mol) at
room temperature. To this reaction mixture was added drop-wise over 30
min 1,2-dibromoethane (10.30 mL, 0.12 mol). Stirring was continued ano-
ther 7 h at room temperature. Ice water (150 mL) was added until preci-
pitating a yellow product, which was recrystallized from ethanol to give (1)
1
(21.20 g, 91.50%), m.p. 79.0–81.0 ꢀC. H NMR (d, CDCl3): 1.37 (t, 3H,
J = 8.0 Hz, CH3-CH2-O-); 2.40 (s, 3H, CH3-); 3.30 (s, 4H, 2 ꢁ -SCH2-);
4.33 (q, 2H, J = 8.0 Hz, -O-CH2-CH3).
2-(1,2-Ethylenedithio)methylene-3-oxo-5-aryl-4-pentenoic
Acids (2)
Compounds (2) were prepared according to a literature method.[12]
General procedure. To a solution of arylaldehyde (10 mmol) and (1)
(2.32 g, 10.0 mmol) in ethanol (50 mL), sodium ethoxide (11 mmol, 0.25 g
sodium dissolved in 5 mL ethanol) was added drop-wise. After that the
reaction mixture was stirred at room temperature overnight. Then the
mixture was poured into cold water (ca. 100 mL). The resulting precipitate
was collected and washed with water. The pure product was obtained by
recrystallization from ethanol.
For the characterization of (2a)–(2c) see Ref. [12].
(2d) Yellow crystals, yield: 3.15 g (93.4%), m.p. 156.0–158.0 ꢀC
(dec). Anal. Calcd. for C14H11NO5S2 (MW 337.37): C, 49.85; H, 3.26; N,
1
4.15%. Found: C, 49.92; H, 3.33; N, 4.02%. H NMR (d, DMSO-d6): 3.43
(s, 4H, 2 ꢁ -SCH2-), 7.14 (d, 1H, J = 16.0 Hz, Ar-CH=CHCO), 7.58 (d,

414
Liang et al.
1H, d, J = 16.0 Hz, Ar-CH=CHCO), 7.93 (d, 2H, J = 8.8 Hz, Ar-H), 8.24
(d, 2H, J = 8.8 Hz, Ar-H), 11.25 (1H, s(br), OH).
(2e) Yellow crystals, yield: 2.80 g (99.2%), m.p. 151.0–153.0 ꢀC (dec).
Anal. Calcd. for C12H10O4S2 (MW 282.34): C, 51.06; H, 3.55%. Found: C,
1
51.11; H, 3.68%. H NMR (d, CDCl3): 3.45 (s, 4H, 2 ꢁ -SCH2-), 6.49 (m,
1H, 4-furanyl-H), 6.59 (d, 1H, J = 15.4 Hz, Ar-CH=CHCO), 7.25–7.50
(m, 3H, Ar-CH=CHCO + 3,5-furanyl-H), OH not observed.
Synthesis of Tributyltin(IV) Carboxylates (3)
All compounds (3a)–(3e) were synthesized using similar procedures,
respectively, and a general procedure is described. A mixture of (n-
Bu3Sn)2O (0.359 g, 1.2 mmol) and (2) (1.0 mmol) and benzene (20 mL)
was refluxed for 4.5 h with stirring. The water liberated in the reaction
was removed azeotropically by a Dean-Stark apparatus. Then the mixture
was cooled to 40 ꢀC and benzene was removed under reduced pressure.
The resulting residue was purified by silica gel (80–120 mesh) chro-
matography (petroleum ether:ethyl acetate = 1:2 (V/V) as an eluent) to
give a pure product.
X-Ray Crystallography
Yellow crystals of (3d) obtained from a mixture solution of pet-
roleum ether and diethyl ether were suitable for a single-crystal X-ray
diffraction study. Diffraction intensities were collected on a Siemens P4
diffractometer fitted with graphite-monochromated MoKa radiation
˚
l = 0.71073 A, employing an o-2q scan technique. Lorentz polarization
and absorption corrections were applied.[13] The structure was solved by
direct methods using the SHELXS 86 program[14] and refined with a full-
matrix least-squares techniques using the SHELXL 93 program.[15] Non-
hydrogen atoms were refined anisotropically. The hydrogen atoms on
carbon atoms were generated geometrically, while the aqua hydrogen atoms
were not located.
RESULTS AND DISCUSSION
Synthesis
2-(1,2-Ethylenedithio)methylene-3-oxo-5-aryl-4-pentenoic acids (2)
were synthesized by condensation of acetylketene dithioacetal (1) with
aryl aldehydes (Figure 1). Pak and co-workers had described the me-
chanism for the formation of (2).[12] The esterification reaction between (2)

Tributyltin(IV) Carboxylates
415
Figure 1. Preparation of aquatributyltin-2-(dialkylthio)methylene-3-oxo-5-aryl-4-
pentenoates.
and bis(tri-n-butyltin)oxide was performed in refluxing benzene, and the tri-
n-butyltin esters (3) were produced in moderate to high yields (Figure 1 and
Table 1). All the compounds synthesized were characterized by their IR
1
spectra (Table 2), H NMR spectra and 13C NMR spectra (Table 3). The
study on the properties of (3) is in progress.
Table 1. Yields and elemental analyses of (3).
Elemental
analysis found
(calcd) (%)
M.p.
(dec) (ꢀC)
Yield
(%)
No.
Formula
State
C
H
(3a)
C26H40O4S2Sn
Yellow oil
–
75.2
82.7
69.8
58.2
66.4
52.17
(52.26)
51.43
6.69
(6.79)
6.98
(3b)
(3c)
(3d)
(3e)
C27H44O5S2Sn
C27H40O6S2Sn
C26H39NO6S2Sn
C24H38O5S2Sn
Red oil
–
(52.31)
50.39
(6.76)
6.23
Yellow
crystals
Yellow
crystals
Red oil
51.0–52.0
68.0–69.0
–
(50.77)
48.52
(6.46)
6.07
(48.84)
48.99
(49.21)
(6.21)
6.46
(6.39)

416
Liang et al.
Table 2. IR data of R1CH=CHCOC(C3H4S2)CO2SnBu3(H2O).
No.
u(COO) asym
u(COO) sym
Du
u(Sn-C)
u(O-H)
(3a)
(3b)
(3c)
(3d)
(3e)
1589
1604
1614
1586
1591
1318
1322
1358
1343
1327
271
282
256
243
264
495
488
490
472
498
3384
3455
3431
3420
3407
Table 3. 1H and 13C NMR data for R1CH=CHCOC(C3H4S2)CO2SnBu3(H2O).
No.
1H NMR (ppm) and 13C NMR (ppm)
(3a)
0.87, 9H (t, J = 8.0 Hz, CH3-); 1.24–1.65, 18H (m, -CH2-); 3.32, 4H
(s, 2 ꢁ -SCH2-); 7.25–7.58, 7H (m, Ar-H + Ar-CH=CHCO).
186.6 ( > C=O), 177.6 (-COO-), 170.7 ( > C= ), 141.0, 135.6, 129.6, 128.6,
128.0, 125.9, 120.5 ( > C= ), 37.7 (-SCH2-), 36.9 (-SCH2-), 27.8, 27.0,
16.8, 13.5 (-CH3).
(3b)
0.87, 9H (t, J = 8.0 Hz, -CH3); 1.20–1.71, 18H (m, -CH2-); 3.31, 4H
(s, 2 ꢁ -SCH2-); 3.82, 3H (s, -OCH3); 6.79–7.54, 6H (m, Ar-H +
Ar-CH=CHCO).
186.4 ( > C = O), 176.4 (-COO-), 170.6 ( > C= ),
160.7, 140.7, 129.5, 128.1, 123.5, 120.5, 113.9 ( > C= ), 55.0 (-OCH3),
37.5 (-SCH2-), 36.7 (-SCH2-), 27.6, 26.8, 16.6, 13.4 (-CH3).
0.87, 9H (t, J = 8.0 Hz, -CH3); 0.95–1.21, 18H (m, -CH2-); 3.31, 4H
(s, 2 ꢁ -SCH2-); 5.97, 2H (s, -OCH2O-); 6.89, 1H (d, J = 12.0 Hz,
Ar-CH=CHCO); 6.71–7.25, 3H (m, Ar-H); 7.42, 1H (d, J = 12.0 Hz,
Ar-CH=CHCO).
(3c)
186.4 ( > C=O), 176.8 (-COO-), 170.6 ( > C= ), 148.9,
148.0, 140.8, 130.0, 124.2, 124.0, 121.0, 108.2, 106.3 ( > C= ), 101.2
(-OCH2O-), 37.6 (-SCH2-), 36.8 (-SCH2-), 27.7, 26.9, 16.9, 13.5 (-CH3).
0.88, 9H (t, J = 8.0 Hz, -CH3); 0.97–1.55, 18H (m, -CH2-); 3.35, 4H
(s, 2 ꢁ -SCH2-); 7.25–8.26, 6H (m, Ar-H + Ar-CH=CHCO).
185.7 ( > C=O), 180.3 (-COO-), 170.5 ( > C= ), 147.9, 142.1, 137.5, 130.1,
128.5, 124.0, 120.1 ( > C= ), 37.9 (-SCH2-), 37.1 (-SCH2-), 27.9, 27.0,
16.9, 13.6 (-CH3).
(3d)
(3e)
0.87, 9H (t, J = 8.0 Hz, -CH3); 1.11–1.66, 18H (m, -CH2-); 3.30, 4H
(s, 2 ꢁ -SCH2-); 6.39–7.39, 5H (m, Furyl-H + Ar-CH=CHCO).
186.2 ( > C=O), 177.2 (-COO-), 170.7 ( > C= ), 152.2, 144.0, 127.6, 123.8,
120.7, 114.4, 112.2 ( > C= ), 37.7 (-SCH2-), 36.9 (-SCH2-), 27.8, 27.0,
16.8, 13.6 (-CH3).

Tributyltin(IV) Carboxylates
417
IR Spectra
It is well known that there are mainly three kinds of coordination types for
trialkyltin carboxylates:[16] the four-coordinate structure (A) for monomers,
the intra-molecular five-coordinated structure (B) for monomers and the inter-
molecular five-coordinated structure (C) for polymers (see Figure 2).
The vacant 5d orbitals in a tin atom tend towards high coordina-
tion numbers with ligands containing lone electron pairs. IR stretching
vibration frequencies of carbonyl groups in organotin carboxylates are
important for determining their structures: when the structure changes from A
to B or C, the asymmetric absorption vibration frequencies (u asym) of
carbonyl groups decrease and the symmetric absorption vibration frequencies
(u sym) increase.[17] The difference [Du (C=O)], therefore, decreases.
From Table 2 we find that the Du values of (3a)–(3e) are between
243–282 cm–1, which suggests a possible tetrahedral structure (A) for
them. However, in the region of 3384–3455 cm–1, strong O—H stretching
modes due to water molecules appeared. Hence, we believe that water
coordination exists in (3a)–(3e) judging from their IR spectra. It should be
noted that the structure reported here is quite different from the three kinds
of coordination types in Figure 2.
NMR Spectra
1H and 13C NMR spectra were recorded in chloroform-d as a solvent
and the spectral assignments are given in Table 3. All Sn(IV) complexes
explored here exhibited similar spectra.
1
In H NMR spectra of (2), a singlet at ca. 3.4 ppm can be attributed to
the protons of ethylenedithio groups. Two doublets which appear in the
range of 6.6–7.7 and 7.5–7.8 ppm may be assigned to the vinylene protons
3
with a three-bond coupling constant JH,H = 16.0 Hz. This is indicative of
a trans carbon—carbon double bond. A broad peak of the carboxy proton is
observed at 8.56 ppm for (2a) and 11.25 ppm for (2d).
1
In H NMR spectra of (3), signals due to the protons of an a-oxoketene
dithioacetal segment shift upfield compared to those of (2). For example,
Figure 2. The coordination types in trialkyltin carboxylates.

418
Liang et al.
Table 4. Crystallographic data for (3d).
(3d)
Formula
M
C52H78N2O12S4Sn2
1288.69
Triclinic
Crystal system
Space group
¯
Pl
˚
l (A)
0.71073
11.148(2)
16.656(3)
18.462(4)
66.379(3)
76.94(3)
87.95(3)
3053.6(11)
2
˚
a (A)
˚
b (A)
˚
c (A)
a ( ꢀ)
b ( ꢀ)
g ( ꢀ)
3
˚
V (A )
Z
Density (mg/mm3)
m (mmꢂ1
1.389
1.010
)
Crystal size (mm)
T ( ꢀC)
0.52 ꢁ 0.42 ꢁ 0.16
20(2)
0.923
Goodness-of-fit on F2
Rint
0.0120
0.0566
0.1644
R1 (I > 2s(I))
WR2 (all data)
˚
Table 5. Selected bond distance (A) and Angles (ꢀ) for (3d).
Sn (1)–C (1)
Sn (1)–O (1)
2.11 (2)
2.15 (3)
2.11 (2)
2.12 (2)
2.49 (2)
2.09 (3)
2.11 (2)
2.20 (3)
2.18 (3)
2.54 (2)
94.7 (10)
125.3 (10)
96.2 (10)
113.0 (10)
91.2 (10)
C (9)–Sn (1)–C (5)
C (1)–Sn (1)–OW1
O (1)–Sn (1)–OW1
C (9)–Sn (1)–OW1
C (5)–Sn (1)–OW1
C (35)–Sn (2)–C (31)
C (35)–Sn (2)–O (6)
C (31)–Sn (2)–O (6)
C (35)–Sn (2)–C (27)
C (31)–Sn (2)–C (27)
O (6)–Sn (2)–C (27)
C (35)–Sn (2)–OW2
C (31)–Sn (2)–OW2
O (6)–Sn (2)–OW2
C (27)–Sn (2)–OW2
113.0 (10)
86.0 (10)
179.1 (7)
83.9 (10)
87.8 (10)
120.4 (12)
94.9 (11)
91.9 (10)
125.2 (11)
112.8 (11)
95.4 (10)
88.4 (11)
85.6 (10)
176.6 (6)
83.6 (10)
Sn (1)–C (9)
Sn (1)–C (5)
Sn (1)–OW1
Sn (2)–C (35)
Sn (2)–C (31)
Sn (2)–O (6)
Sn (2)–C (27)
Sn (2)–OW2
C (1)–Sn (1)–O (1)
C (1)–Sn (1)–C (9)
O (1)–Sn (1)–C (9)
C (1)–Sn (1)–C (5)
O (1)–Sn (1)–C (5)

Tributyltin(IV) Carboxylates
419
the protons of the ethylenedithio groups at ca. 3.4 ppm in free acids shift to
ca. 3.3 ppm in tributyltin carboxylates. The protons of the methyl groups in
the butyl groups are observed at ca. 0.8 ppm as triplets, while the protons
of the methylene groups in the butyl groups are observed at 0.95–1.71 ppm
as multiplets.
In 13C NMR spectra, these complexes give signals at 185.7–186.6
ppm due to carbonyl carbon atoms and 176.4–180.3 ppm due to carboxy
carbon atoms. The signals of the carbon atoms of benzene rings and
vinylene are observed in the range of 112.2–170.7 ppm. The signals at
36.7–37.9 ppm are attributed to the carbon atoms of ethylenedithio groups.
The signals due to the butyl groups are in the range of 13.4–27.9 ppm.
The tin–carbon coupling peaks can be seen clearly. The coupling constants
1
2
are J119/117Sn-13C = 680 Hz and J119/117Sn-13C = 128 Hz, respectively.
Figure 3. Molecular Structure of (3d).

420
Liang et al.
˚
Table 6. Sn–Owater distances (A) in aquatin(IV) complexes.
˚
Sn–Owater (A)
Compound
Ref.
[18]
[19]
PyCO2Sn(CH3)3(H2O)
(CH3)3Sn(NO2)(H2O)
PhSO3Sn(CH3)3(H2O)
2.433
2.47
2.301
2.492, 2.542
[20]
This work
4-NO2-C6H4CH CHCOC(C3H4S2)
CO2Sn(C4H9)3(H2O)
Crystal Structure of (3d)
The crystallographic and experimental data for (3d) is listed in Table 4
and the selected bond sistance and angles for (3d) listed in Table 5. The
crystal structure with numbering scheme of (3d) is shown in Figure 3. In
the molecule each tin atom is coordinated to three carbon atoms of three
butyl groups in an equatorial position and two oxygen atoms, one from a
carboxylate group and the other from a water molecule, in an axial
position, forming a distorted trigonal bipyramidal structure containing
water of coordination. This is another proof of having a water molecule in
the product. As listed in Table 3, ff C(1)Sn(1)C(5) + ff C(5)Sn(1)C(9) +
ff C(9)Sn(1)C(1) = 358.5ꢀ which is nearly 360ꢀ. This indicates that the
C(1), C(5), C(9) and Sn atoms are close to being coplanar. Two oxygen
atoms occupy an axial position and the principal axis is almost linear with
an O(1)-Sn(1)-OW(1) angle of 179.1ꢀ. The tin coordination environment
slightly deviates from the ideal trigonal bipyramidal conformation.
˚
In (3d), the bond lengths of Sn(1)–OW1 and Sn(2)–OW2 are 2.492 A
˚
and 2.542 A, respectively. The tin–water bond distance is only slightly
larger than that in other aquatin(IV) complexes (Table 6).[18–20]
ACKNOWLEDGMENTS
This work is financed by the National Natural Science Foundation of
China (No. 29862004).
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Received:November 28, 2001
Accepted:October 28, 2002
Referee I:T. Kawatoh
Referee II:K. Sakata