1H, 13C, and 119Sn NMR, IR, mass, thermal, and biological studies of organotin(IV) derivatives of 4-p-(chlorophenyl)-2-phenyl-5-thiazoleacetic acid

Article abstract of DOI:10.1081/SIM-120014856

A series of di- and triorganotin(IV) carboxylates of 4-p-(chlorophenyl)-2-phenyl-5-thiazoleacetic acid has been synthesized and characterized by various instrumental techniques such as infrared, ¹H, ¹³C, ¹¹⁹Sn NMR, mass spectrometry and thermal analysis. These compounds were also tested for their antibacterial and antifungal activities to study their biological significance.

Full text of DOI:10.1081/SIM-120014856

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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 32, No. 8, pp. 1373–1392, 2002
1H, C, AND 119Sn NMR, IR, MASS,
13
THERMAL, AND BIOLOGICAL STUDIES
OF ORGANOTIN(IV) DERIVATIVES OF
4-p-(CHLOROPHENYL)-2-PHENYL-5-
THIAZOLEACETIC ACID
Saqib Ali,1,* M. Nawaz Khokhar,2 M. H. Bhatti,1
M. Mazhar,1 M. Tariq Masood,1 Khadija Shahid,1 and
Amin Badshah1
1Department of Chemistry, Quaid-i-Azam University,
Islamabd 45320, Pakistan
2National Physical and Standard Laboratory, 16-H=9,
Islamabad, Pakistan
ABSTRACT
A series of di- and triorganotin(IV) carboxylates of 4-p-
(chlorophenyl)-2-phenyl-5-thiazoleacetic acid has been syn-
thesized and characterized by various instrumental techniques
such as infrared, 1H, 13C, 119Sn NMR, mass spectrometry and
thermal analysis. These compounds were also tested for their
*Corresponding author. E-mail: drsa54@yahoo.com
1373
DOI: 10.1081=SIM-120014856
Copyright # 2002 by Marcel Dekker, Inc.
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com

1374
ALI ET AL.
antibacterial and antifungal activities to study their biological
significance.
INTRODUCTION
Organotin compounds of oxygen and nitrogen donor ligands are well
known for their biological activity.[174] Recently, organotin(IV) complexes
of sulfur-containing ligands have received considerable attention.[5,6] In view
of the diverse fields of applications of organotin complexes, we have syn-
thesized and characterized a number of organotin complexes with various
donor ligands.[7714] Some of these were subjected to X-ray crystal analy-
sis[15718] and have found biological[19,20] and industrial applications.[21] In
continuation of our previous work we have synthesized some complexes of
the general formulae R2SnL2 and R3SnL, L ¼ 4-p-(chlorophenyl)-2-phenyl-
5-thiazole acetic acid anion (Fig. 1). These complexes have been char-
acterized by elemental analyses, infrared, multinuclear (1H, 13C, 119Sn)
NMR and mass spectrometry. Thermal analysis was performed for the
complexes to study their energy of activation and order of decomposition
reactions. The compounds showed high activity against various bacteria and
fungi. The crystal analysis for Me3SnL shows the coordination of one H2O
molecule with the Sn atom.[22]
RESULTS AND DISCUSSION
The reported compounds of type (a) and (b) were prepared by the
reaction of the ligand salt (method I) with the respective organotin chlorides
[Eqs. (1) and (2)] or by the reaction of ligand acid (method II) and organ-
otinoxide or hydroxide [Eqs. (3) and (4)].
Figure 1. Structure of the ligand (HL).

ORGANOTIN(IV) DERIVATIVES
1375
R2SnCl2 þ 2NaL ꢀ! R2SnL2 þ 2NaCl
R3SnCl þ NaL ꢀ! R3SnL þ NaCl
R2SnO þ 2HL ꢀ! R2SnL2 þ H2O
R3SnOH þ HL ꢀ! R3SnL þ H2O
ð1Þ
ð2Þ
ð3Þ
ð4Þ
Type (a) R2SnL2
Compound No.
R
(1)
(2)
(3)
(4)
(5)
Me
Et
n-Bu
Ph
Bz
Type (b) R3SnL
Compound No.
R
(6)
Me
(7)
n-Bu
(8)
Ph
(9)
Bz
All the compounds are colourless crystalline solids. Their physical data, i.e.,
melting points, % yield and CHN analysis are reported in Table I.
Infrared Spectroscopy
The infrared spectra have been recorded in the range of 4000-250 cmꢀ1
as KBr=CsBr discs and important bands for structural assignments are
given in Table II. The broad band at 293072590 cmꢀ1 due to n(OH) present
in the spectrum of the ligand is absent in the spectra of the corresponding
organotin derivatives, thus showing deprotonation of the carboxylic acid
group. The Dn values [Dn ¼ nasym(COO)ꢀnsym(COO)] has been used to
predict the mode of tin carboxylate interaction.[23] There is donation of
charge density from C¼O:? to the electropositive tin metal, which slightly
increase the C¼O bond length, hence, the absorption frequency decreases
and carboxylate acts as bidentate ligand in the solid state. The complexation
of tin(IV) with the ligand is further confirmed by the absence of Sn–Cl
vibrations at ca. 333 cmꢀ1, and the presence of Sn–O bands in the range
450ꢀ500 cmꢀ1
.

1376
ALI ET AL.
Table I. Physical Data for Organotin(IV) Carboxylatesa
Compound Molecular Formula
No.
M.p.
(ꢁC)
Yield
(%)
%C %H
Cald.=Exp. Cald.=Exp.
(Formula Weight)
(1)
C36H28Cl2N2O4S2Sn
(806)
C38H32Cl2N2O4S2Sn
(834)
C42H40Cl2N2O4S2Sn 123724
(890)
C46H32Cl2N2O4S2Sn
(930)
C48H36Cl2N2O4S2Sn 1087110
(958)
C20H22ClNO3SSn
(510.5)
C29H38ClNO2SSn
(618.5)
82783
95797
70
79
83
84
78
73
70
78
80
53.60=53.77
54.68=54.95
56.62=55.96
59.35=58.88
60.12=60.05
47.01=46.70
56.26=55.90
61.90=62.00
63.29=63.42
3.47=3.60
3.84=3.92
4.44=4.22
3.44=3.85
3.76=4.09
4.31=3.95
6.14=6.38
3.83=4.12
4.44=4.72
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
96797
71772
141742
84785
91792
C35H26ClNO2SSn
(678.5)
C38H32ClNO2SSn
(720.5)
aCompound (6) contains an H2O molecule.
Table II. Infrared Data for the Investigated Compoundsa
Compounds
n(COO)asym
n(COO)sym
Dn
n(Sn7C)
n(Sn7O)
(1)
(2)
(3)
(4)
(5)
(6)
(7)
(8)
(9)
1632 s
1625 s
1616 s
1614 s
1631 s
1619 s
1610 s
1616 s
1614 s
1442 s
1437 s
1440 s
1456 s
1440 s
1430 s
1430 s
1460 s
1452 s
190
188
176
158
191
184
180
156
162
555 s, 522 w
580 s, 535 m
556 w, 528 m
556 s
570 w, 530 m
554 w, 520 w
582 m, 528 m
548 w, 504 w
558 s, 508 w
468 w
472 w
465 m
482 s
479 m
460 m
462 w
460 m
470 w
as, strong; m, medium; w, weak.

ORGANOTIN(IV) DERIVATIVES
1377
NMR
1H NMR spectra of the investigated compounds show the absence of
OH signals at 11.0 ppm for COOH of the ligand which indicate the
bonding of tin with the ligand moiety through the deprotonated carboxylic
oxygen. The ligand shows a complex pattern for aromatic protons which
remains almost the same in the tin compounds (Table III). However,
additional signals due to the organic groups attached to tin appear in the
region 0.571.7 ppm (R ¼ Me, Et, Bu) and 7.577.8 ppm (R ¼ Ph, Bz). The
n
13C and 119Sn NMR data, along with the coupling constants J(119Sn, 13C)
are listed in Table III. Deshielding of the protons H(11) and (15) and
H(12) and (14) is observed in all complexes which should be due to the
electropositive nature of the tin. A s-charge donation from the COOꢀ
donor to the tin atom decreases the electron density of the ligand and
produces deshielding. All the shifts are downfield except for H(2) and (6),
H(3) and (5) and H(13) which are shifted upfield, probably due to the ring
current effect.
The involvment of the carboxylic group in bonding to tin is
confirmed by the resonances ascribed C(16) and C(8) which exhibit the
greatest shifts upon coordination (Table IV). The remaining resonances
due to the aromatic carbon atoms do not shift significantly on bonding
to tin. The greatest downfield shift is observed for the carboxylic carbon,
C(17), while all the remaining carbon atoms shift downfield by
ꢂ0.876.0 ppm.
1
Using the J values in Lockhart’s equation,[24] in compounds (1), (3),
(6) and (7) the predicted C–Sn–C angles are 131.5, 131.5, 110 and 110.9ꢁ,
respectively, which confirms the characteristic tetrahedral environment of
tin in non-coordinating solvents.
The values of d 119Sn define the region of various coordination num-
bers of the central tin atom.[5] According to data in Table IV, all compounds
show a tetrahedral environment around tin in solution (Fig. 2).
Thermal Studies
The degradation of organotin complexes gave identical patterns of
decomposition. Horowitz[25] and Coats and Redfern[26] formulae were used
for TG curves to determine the energy of activation (Ea) and order of
reaction (n).
The ligand decomposes in two steps. In the first step CH3COOH,
ꢁ
C6H5Cl and C6H5CN evolve over the temperature range of 2307400 C.
The order of the reaction is ‘‘0’’ and the energy of activation is

1378
ALI ET AL.

ORGANOTIN(IV) DERIVATIVES
1379

1380
ALI ET AL.
Figure 2. Proposed structures (a) for triorganotin(IV) carboxylates and (b) for
diorganotin(IV) dicarboxylates in non-coordinating solvents.
18.42 kcal=mol. Inꢁthe second step only sulfur evolves in the temperature
range of 4707595 C. The order of this step is also ‘‘0’’ and the energy of
activation is 6.84 kcal=mol. The residue contains only carbon in this case.
The thermal degradation of compounds (6) and (4) takes place in three
steps, whereas the remaining compounds decompose in two steps. The
various fragments evolved, their activation energy and order of reactions
are reported in Tables V and VI.
Mass Spectrometry
The monoisotopic mass fragmentation of the individual compounds
are reported in the experimental section. The molecular ion peak of these
complexes has not been observed like in previous reports.[27,28] Two
representative compounds and the ligand are discussed here for their
mass fragmentation while the remaining compounds follow an analogous
patterns. The primary fragmentation of the ligand takes place due to the
loss of the carboxylate group followed by two routes of fragmentation: (i)
loss of chlorine forming [C16H11NS]þ and subsequent loss of C9H6S and

ORGANOTIN(IV) DERIVATIVES
1381
Table V. Proposed Degradation Pattern for Organotin(IV) Carboxylates
Weight Loss
%
Temp. Range
(ꢁC)
Evolved
Compd.
Remaining
Compd.
Calcd. Obs.
Compound
HL
2307400
CH3COOH,
C6H5Cl,
C6H5CN
S
83.6
84.0
C2S
2C
4707595
09.70 08.60
(3)
(4)
2707456
4987718
C16H11ClNS
C17H11ClNO2S
CO
SnC26H29ClNO4S 32.00 32.26
40.10 40.33
Bu2SnO
557360
3607480
5207735
L
PhC9H4ClNS
Ph
Ph2SnL
PhSnCOOCH2
SnCOOC
35.30 37.96
29.11 30.26
08.29 07.96
(6)
(7)
(8)
(9)
1967500
5607690
3Me, H2O
SnC17H11ClNO2S 12.33 12.20
SnO2 66.07 65.72
SnC17H11ClNO2S 27.67 29.33
C17H11ClNS
2877480
5307625
3Bu
C17H11ClNS
SnO2
47.98 46.09
2007545
5457665
C16H12ClNS
2Ph, CO2
Ph3SnO2C
PhSn
41.11 42.45
29.20 29.39
2177510
5247728
C15H11ClNS
2Bz, C6H5
Bz3SnOOC
SnC2H2O2
39.51 39.25
35.97 36.11
CN forming [C6H5CN]þ and [C6H5]þ ions, respectively and (ii) loss of
C6H5CN forming [C9H6SCl]þ and subsequent loss of CS and C2HCl
forming [C8H6Cl]þ and [C6H5]þ ions, respectively. A third route was
observed by the loss of chlorine from [C9H6SCl]þ and C6H5CN from
[C16H11NS]þ with the formation of [C9H6S]þ at m=z 146 which on fur-
ther loss of C2H2 results in [C7H4S]þ ion at m=z 120. The fragmentation
pattern of the ligand is given in Fig. 3.
The compound (6) follows two routes of fragmentation. In the first
route it gives a peak at m=z 478 after the loss of one methyl radical, which
further gives a peak of the ligand ion at m=z 328 after losing the Sn(CH3)2
radical. The ligand ion adopts almost the same pattern of fragmentation as
given in Fig. 3. In the second route, the compound shows a peak of
[Sn(CH3)3]þ at 165 which gives a peak of [Sn]þ at 120 after loosing 3 CH3
radicals (Fig. 4).

1382
ALI ET AL.
Table VI. Energy of Activation and Order of Reaction for Organotin(IV) Car-
boxylatesa,b
Redfern’s
Method
Temp. Range
(ꢁC)
Ts (ꢁC)
Horowitz (Ea)
Ea
n
Compound
L
3167400
5117576
2767457
4907710
567360
3607480
5217720
1947500
5677686
2967466
4967593
1947342
5187560
2167482
5007728
361.92
556.8
27.92
18.25
22.98
42.05
17.86
14.27
22.12
17.45
25.96
21.60
40.87
33.44
22.31
26.53
26.60
28.90
14.18
18.81
39.24
18.23
16.96
25.23
16.84
24.77
22.04
36.97
34.83
25.94
27.74
22.77
1.25
1.00
0.75
1.00
1.00
1.25
0.80
1.00
1.00
0.66
1.00
1.00
1.25
1.25
1.25
(3)
(4)
312.65
633.75
288.30
362.70
585.20
287.64
583.74
329.94
558.36
258.26
583.30
274.85
595.35
(6)
(7)
(8)
(9)
aEa ¼ Energy of activation Kcal=mol.
bn ¼ Order of the reaction.
Compound (3), after giving rise to the fragments [C17H11Cl-
NO2SSnBu2]þ at m=z 562 and [C17H11ClNO2SSn]þ at m=z 448 fragments by
two routes. In the first route, the ligand ion is formed after losing an Sn
radical, which undergoes fragmentation almost in the same way as in Fig. 3.
Whereas the second route ends with [Sn]þ at m=z 120, after giving rise to
different fragments at their respective m=z values.
Biological Activity
Biological activity tests of the compounds were carried out against
various bacteria and fungi by the ‘‘agar diffusion technique’’.[29] All the
compounds were screened for antibacterial and antifungal activity. The
results are given in Tables VII and VIII.
The screening test shows that the butyl and phenyltin carboxylates are
the most potent candidates against the tested bacteria. The activity of the

ORGANOTIN(IV) DERIVATIVES
1383
Figure 3. Proposed mass fragmentation pattern of the ligand.
other derivatives varies according to their R groups. However, all of these
compounds are active against E. coli (Table VII).
Earlier reports show that higher antifungal activity is associated with
tributyltin and triphenyltin compounds.[30] In the present case most of the
compounds show high antifungal activity against the tested fungi. Fentiazac
is also active against some species of the tested fungi while in some cases like
Aspergillus niger, it is inactive, but trimethyl- and tributyltin derivatives are
highly active against this fungus. In the present series diphenyltin, tri-
benzyltin and dibenzyltin carboxylates, comparatively, are more active
(Table VIII).
Brine Shrimps (Artemia salina), a tiny crustacean, have been used
for the determination of toxicity of the organotin carboxylates. The
results are given in Table IX. Previous reports[30,31] show that the toxicity
of organotin compounds depends upon the nature of the organic group.
The highest toxicity being shown by compounds having three tin carbon
(Sn–C) bonds.

1384
ALI ET AL.
Figure 4. Proposed mass fragmentation pattern for compound (6).
EXPERIMENTAL
Chemicals
All solvents used were purchased from Merck, Germany and were
dried before use according to the standard methods.[32] Di- and triorganotin
chlorides were purchased from Aldrich, USA, whereas organotin oxides and
hydroxides were obtained from Strem, USA. All of these chemicals were of
analytical reagent grade and were used without further purification.
4-( p-Chlorophenyl)-2-phenyl-5-thiazoleacetic acid (Fentiazac=Donoerest)
was kindly provided by Wyeth Pharmaceutical Co. Ltd., Pakistan, and was
recrystallized from benzene and dried over P2O5 under vacuum (m.p.
161762 ꢁC).

ORGANOTIN(IV) DERIVATIVES
1385
Table VII. Antibacterial Activity of Organotin(IV) Carboxylatesa7c
Bacterium
(3) (4) (5) (6) (7) (8) (9) HL S1 S2
Corynebacterium diptheriae 16
13
13
15
9
8
n.a. 11
n.a.
14
14
15
6
7
7
6
6
6
6
7
6
13 12
17 18
18 19
18 17
18 19
16 17
Streptococcus ryogenes
Streptococcus aureus
Proteus mirabillis
7
12
7
10 n.a. 16
12 n.a. n.a. n.a. n.a. n.a. n.a.
Escherichia coli
Shigella boydii
Pseudomonas aeroginosa
12
7
12
n.a.
8
6
7
7
n.a.
n.a.
14
7
8
6
n.a.
8
6
8
n.a. n.a.
8
n.a. 19 18
aInhibition zone in mm, 100 mg=100 mL.
bS1 and S2, Standards ampicilline and tobramycine, 10 mg=100 mL.
cn.a., No activity.
Table VIII. Antifungal Activity for Organotin(IV) Carboxylatesa7c
Organotin Carboxylates
Fungus
HL
(3)
(4)
(5)
(6)
(7)
(8)
(9)
Allescheria boydii
Aspergillus niger
Candida albicans
Curvularia lunata
Drechslera restrata
Nigrospora oryzae
Microsporum canis
Pleurotus ostreatus
Stachybotrys atra
þþþ
7
7
7
7
7
þ
þþþ þþþ
7
7
7
7
7
þþþ
7
þþ
7
þþþ þþþ
þ
7
þ
7
7
þþ
þþþ
þþþ
7
þþ þþ þþþ þþþ þþþ
7
þþþ þþþ þþþ þþþ
þþþ þþþ þþþ
þþþ þþþ
7
7
7
þþþ
7
7
þþ
þþþ þþþ þþþ
7
þþþ
þþþ þþþ þþþ þþþ þþþ
7
þþþ þþþ
þþ
7
þ
þþ þþþ þþþ þþþ
7
7
þþþ
þþþ
Trichophyton mentagophyte þþþ
þþþ þþþ þþþ
7
aStrong inhibition (þþþ) (60780%); medium inhibition, (þþ) (50760%); weak
inhibition, (þ) (30750%); no inhibition (ꢀ).
b
ꢁ
Incubation period, 7710 days; incubation temp., 27729 C.
cMedium used: Sabouraud Dextrose Agar; Conc. used for sample, 200 mg=mL of
medium.
Instrumentation
Melting points were determined in capillary tubes using an electro-
thermal melting point apparatus model MP-D Mitamura Riken Kogyo
(Japan) and are uncorrected. Infrared spectra were recorded within the

1386
ALI ET AL.
Table IX. Toxicity Data for Organotin(IV) Carboxylatesa
Toxicity
Compound
Upper Value
Lower Value
LD50
HL
(3)
(4)
(5)
(6)
(7)
(8)
(9)
7
7
>100
1.5089
0.2126
>100
1.9266
0.8197
0.3404
>100
2.3652
2.3474
7
3.0608
1.4535
1.6801
7
0.8677
0.4724
7
1.2884
0.2400
0.5953
7
aUpper value ¼ dose in mg=mL at which maximum organisms die; Lower
value ¼ dose in mg=mL at which death of organism starts; LD50 ¼ Lethal dose at
which 50% organisms die.
range 40007600 cmꢀ1 in KBr and 6007200 cmꢀ1 in CsBr pellets on a Perkin
Elmer 3300 spectrometer (USA). The 1H, 13C and 119Sn NMR spectra
were recorded on a Bruker ARX 250 spectrometer (Germany), using CDCl3
as an internal reference for 1H and 13C [d 1H (CDCl3) ¼ 7.24: d 13C
(CDCl3) ¼ 77.0] and Me4Sn as external reference for 119Sn [X (Sn) ¼
37.290665]. Thermal analysis were carried out in nitrogen (N2) by a Netzsch
simultaneous thermal analyzer STA-429 while mass data were recorded on a
70 eV mass spectrometer model MAT 8500 Finnigan (Germany).
Synthesis
Since organotin halides and their derivatives are air- and moisture-
sensitive; all glassware was completely dried at 140 ꢁC and reactions were
carried out under argon. Two synthetic routes were used for the preparation
of complexes.
Method (a) Sodium ethoxide was prepared by reacting 100 mL of
ethanol with 0.1 mole (2.3 g) of sodium metal in a two-neck 250 mL round
bottom flask equipped with a condenser, ice bath and magnetic stirrer. After
completion of the reaction 0.1 mole (32.98 g) of the ligand acid was added to
it. The mixture was refluxed for 374 h and after cooling the appropriate
organotin chloride (0.1 mole in the case of triorganotin compounds and

ORGANOTIN(IV) DERIVATIVES
1387
0.05 mole in the case of diorganotin compounds) was added with constant
stirring. The mixture was refluxed for 576 h and was allowed to stand
overnight at room temperature. The sodium chloride formed was filtered
and ethanol was removed under reduced pressure and the solid formed was
recrystallized from an appropriate solvent.
Method (b) Stoichiometric amounts of the ligand acid (0.01 mole,
3.298 g) and organotin oxide (0.005 mole) or hydroxide (0.01 mole) were
refluxed in 100 mL dry toluene for 374 h. Water formed was continuously
removed using a Dean and Stark apparatus. Toluene was then removed
completely under reduced pressure in a high vacuum. The residue was
treated with activated charcoal in chloroform and filtered. The filtrate was
ꢁ
concentrated and kept at low temperature (ꢀ5 C). The formed solid mass
was recrystallized from an appropriate solvent.
Compound (1)
Recrystallized from dichloromethane. MS, m=z (%) [fragment]: 806
(not observed) [Me2Sn(C17H11ClNO2S)2]þ, 791 (78) [MeSn(C17H11Cl-
NO2S)2]þ, 776 (62) [Sn(C17H11ClNO2S)2]þ, 476 (100) [Me2 Sn(C17H11-
ClNO2S)]þ, 463 (55) [Me Sn(C17H11ClNO2S)]þ, 448 (40) [Sn(C17H11-
ClNO2S)]þ, 404 (32) [Sn(C16H11ClNS)]þ, 328 (45) [C17H11ClNO2S]þ, 284
(36) [C16H11ClNS]þ, 276 (21) [C17H10NOS]þ, 249 (15) [C16H9OS]þ, 181 (37)
[C9H6ClS]þ, 150 (52) [Me2Sn]þ, 146 (18) [C9H6S]þ, 120 (28) [Sn]þ.
Compound (2)
Recrystallized from dichloromethane. MS, m=z (%) [fragment]: 834
(not observed) [Et2Sn(C17H11ClNO2S)2]þ, 805 (20) [EtSn(C17H11ClNO2-
S)2]þ, 776 (35) [Sn(C17H11ClNO2S)2]þ, 477 (25) [EtSn(C17H11 ClNO2S)]þ,
448 (55) [Sn(C17H11ClNO2S)]þ, 404 (100) [Sn(C16H11ClNS)]þ, 328 (60) [C17-
H11ClNO2S]þ, 311 (32) [C17H10ClNOS]þ, 276 (27) [C17H10 NOS]þ, 249 (22)
[C16H9OS]þ, 181 (37) [C9H6ClS]þ, 149 (38) [C6H6Cl]þ, 120 (28) [Sn]þ.
Compound (3)
Recrystallized from dichloromethane and n-hexane (1:1). MS, m=z
(%) [fragment]: 890 (not observed) [(C17H11ClNO2S)2SnBu2]þ, 562 (90)
[(C17H11ClNO2SSnBu2]þ, 448 (20) [(C17H11ClNO2SSn]þ, 328 (30) [(C17-
H11NO2ClS)]þ, 312 (72) [SnC10H8SO2]þ, 284 (85) [C16H11ClNS]þ, 236 (42)

1388
ALI ET AL.
[SnC4H4O2S]þ, 181 (63) [C9H6SCl]þ, 149 (100) [C9H6Cl]þ, 120 (38) [Sn]þ, 69
(87) [HC3S]þ, 32 (64) [S]þ.
Compound (4)
Recrystallized from dichloromethane and n-hexane (1:1). MS, m=z
(%) [fragment]: 930 (not observed) [(Ph)2 Sn(C17H11ClNSO2)2]þ, 602 (5)
[(Ph)2SnC17H11ClNO2S]þ, 567 (20) [(Ph)2SnC17H11NO2S]þ, 328 (5)
[C17H11ClNO2S]þ, 312 (65) [PhSnC5H7OS]þ, 284 (27) [C16H11ClNS]þ, 249
(12) [C6H5SnSOH4]þ, 181 (15) [C9H6SCl]þ, 120 (10) [Sn]þ, 77 (100)
[C6H5]þ.
Compound (5)
Dibenzyltin dichloride was prepared by the reported method.33 The
Compound (5) was recrystallized from dichloromethane. MS, m=z (%)
[fragment]. 958 (5) [(Bz)2Sn(C17H11NO2ClS)2]þ, 867 (35) [(Bz)-
Sn(C17H11NO2ClS)2]þ, 776 (58) [Sn(C17H11NO2ClS)2]þ, 539 (100)
[(Bz)Sn(C17H11NO2ClS)]þ, 448 (25) [Sn(C17H11NO2ClS)]þ, 404 (42)
[SnC16H11 ClNS]þ, 328 (32) [C17H11ClNO2S]þ, 311 (100) [C17H10ClNOS]þ,
276 (13) [C17H10NOS]þ, 249 (18) [C16H9OS]þ, 181 (39) [C9H6SCl]þ, 149 (22)
[C9H6Cl]þ, 120 (41) [Sn]þ.
Compound (6)
Recrystallized from dichloromethane. MS, m=z (%) [fragment]: 511
(not observed) [C17H11ClSNO2Sn(CH3)3H2O]þ, 478 (12) [C17H11ClSNO2-
Sn(CH3)2]þ, 311 (25) [C17H11NSO2H2O]þ, 328 (10) [C17H11ClNO2S]þ, 284
(40) [C16H11ClNS]þ, 249 (18) [C16H11NS]þ, 181 (30) [C9H6SCl]þ, 165 (100)
[(CH3)3Sn]þ, 146 (35) [C9H6S]þ, 137 (20) [C8H6Cl]þ, 120 (10) [Sn]þ, 103 (12)
[C6H5CN]þ, 77 (8) [C6H5]þ.
Compound (7)
Recrystallized from dichloromethane. MS, m=z (%) [fragment]: 619
(not observed) [C17H11ClNO2SSn(Bu)3]þ, 489 (3) [C20H16SNClO2Sn]þ, 402
(40) [(Bu)C10H6O2SClSn]þ, 375 (14) [C12H12SClO2Sn]þ, 328 (28) [C17H11-
ClNO2S]þ, 312 (85) [C10H5ClO2Sn]þ, 284 (40) [C16H11ClNS]þ, 249 (17)

ORGANOTIN(IV) DERIVATIVES
1389
C16H11NS]þ, 181 (30) [C9H6SCl]þ, 120 (27) [Sn]þ, 90 (47) [C7H6]þ, 69 (100)
[C3HS]þ, 32 (24) [S]þ.
Compound (8)
Recrystallized from chloroform and dichloromethane (1:1). MS, m=z
(%) [fragment]: 679 (not observed) [(Ph)3Sn(C17H11NO2ClS)]þ, 602 (75)
[(Ph)2SnC17H11NO2ClS]þ, 567 (24) [(Ph)2SnC17H11NO2S]þ, 533 (10)
[(Ph)2SnC17H9NO2]þ, 328 (7) [C17H11ClNO2S]þ, 312 (28) [PhSnC5H7OS]þ,
284 (20) [C16H11ClNS]þ, 274 (75) [(Ph)2Sn]þ, 181 (19) [C9H6SCl]þ, 197 (7)
[(Ph)Sn]þ, 168 (64) [C8H5SCl]þ, 134 (30) [C8H3Cl]þ, 120 (12) [Sn]þ, 103 (43)
[C6H5CN]þ, 89 (33) [C7H5]þ, 77 (24) [C6H5]þ.
Compound (9)
Tribenzyltin chloride was prepared by the reported method.33 The
compound (9) was recrystallized from dichloromethane. MS, m=z (%)
[fragment]: 721 (not observed) [(Bz)3SnC17H11NO2ClS]þ, 563 (50) [(Bz)3-
SnC7H5ClNO2]þ, 539 (8) [(Bz)SnC17H11NO2ClS]þ, 448 (11) [SnC17H11-
ClNO2S]þ, 404 (4) [SnC16H11ClNS]þ, 328 (18) [C17H11ClNO2S]þ, 311 (100)
[C17H10ClNOS]þ, 276 (33) [C17H10NOS]þ, 249 (21) [C16H9OS]þ, 181 (33)
[C9H6SCl]þ, 149 (50) [C9H6Cl]þ, 120 (15) [Sn]þ.
ACKNOWLEDGMENTS
We are thankful to Prof B. Wrackmeyer, University of Bayreuth,
Germany, for providing multinuclear NMR and mass facilities. SA is
indebted to the Quaid-i-Azam University for financial support of the work
under a University Research Fund program and the Alexander von Hum-
boldt foundation for awarding the Georg Forster Research Fellowship.
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Received February 21, 2002
Accepted May 28, 2002
Referee I: M. K. Denk
Referee II: J. M. Iriarte-Gross