Di- and tri-organotin(IV) complexes of the new bis(1-methyl-1H-imidazol-2-ylthio)acetate ligand and the decarboxylated analogues

Article abstract of DOI:10.1016/j.jorganchem.2007.12.021

The new sodium bis(1-methyl-1H-imidazol-2-ylthio)acetate, Na[(S-tim)₂CHCO₂], has been prepared in ethanol solution using 2-mercapto-1-methylimidazole, dibromoacetic acid and NaOH. New di- and tri-organotin(IV) derivatives have been synthesized from reaction between SnR_nCl_4-n (R = Ph, Cy and ⁿBu, n = 2-3) acceptors and Na[(S-tim)₂CHCO₂]. Complexes of the type {[κ¹O-(S-tim)₂CHCO₂]SnR₃} and related decarboxylated species {[κ²N,N-(S-tim)₂CH₂]SnR₂Cl₂} have been obtained and characterized by elemental analyses, FT-IR, ESIMS and multinuclear (¹H, ¹³C and ¹¹⁹Sn) NMR spectral data. The adduct {κ¹O-[(S-tim)₂CHCO₂]Sn(H₂O)(C₄H₉)₃} was characterized by single crystal X-ray studies. The dichloromethane reaction solution of {κ¹O-[(S-tim)₂CHCO₂]Sn(C₆H₅)₃} was re-crystallized and the decarboxylated species {[(S-tim)₂CH₂]SnCl(H₂O)(C₆H₅)₃} was obtained as a crystalline solid and characterized by X-ray crystallography.

Full text of DOI:10.1016/j.jorganchem.2007.12.021

Available online at www.sciencedirect.com
Journal of Organometallic Chemistry 693 (2008) 996–1004
www.elsevier.com/locate/jorganchem
Di- and tri-organotin(IV) complexes
of the new bis(1-methyl-1H-imidazol-2-ylthio)acetate ligand
and the decarboxylated analogues
a,
a
b
a
*
Maura Pellei , Simone Alidori , Franco Benetollo , Giancarlo Gioia Lobbia ,
Marilena Mancini a, Gaia Emanuela Gioia Lobbia c, Carlo Santini a
a
`
Dipartimento di Scienze Chimiche, Universita di Camerino, via S. Agostino 1, 62032 Camerino (MC), Italy
b ICIS-C.N.R., Corso Stati Uniti 4, 35127 Padova, Italy
`
Scuola di Specializzazione in Farmacia Ospedaliera, via Lili 55, Universita di Camerino, Camerino (MC), Italy
c
Received 14 October 2007; received in revised form 12 December 2007; accepted 12 December 2007
Available online 23 December 2007
Abstract
The new sodium bis(1-methyl-1H-imidazol-2-ylthio)acetate, Na[(S-tim)2CHCO2], has been prepared in ethanol solution using 2-mer-
capto-1-methylimidazole, dibromoacetic acid and NaOH. New di- and tri-organotin(IV) derivatives have been synthesized from reaction
between SnRnCl4ꢀn (R = Ph, Cy and nBu, n = 2–3) acceptors and Na[(S-tim)2CHCO2]. Complexes of the type {[j1O-(S-tim)2CH-
CO2]SnR3} and related decarboxylated species {[j2N,N-(S-tim)2CH2]SnR2Cl2} have been obtained and characterized by elemental
analyses, FT-IR, ESIMS and multinuclear (1H, 13C and 119Sn) NMR spectral data. The adduct {j1O-[(S-tim)2CHCO2]Sn(H2O)(C4H9)3}
was characterized by single crystal X-ray studies. The dichloromethane reaction solution of {j1O-[(S-tim)2CHCO2]Sn(C6H5)3} was
re-crystallized and the decarboxylated species {[(S-tim)2CH2]SnCl(H2O)(C6H5)3} was obtained as a crystalline solid and characterized
by X-ray crystallography.
Ó 2007 Elsevier B.V. All rights reserved.
Keywords: Organotin(IV); Scorpionates; Methimazole; X-ray; Spectroscopy
1. Introduction
generally high selectivity of organotin reagents allows one
to save time and to avoid product losses of protection–
deprotection cycles. In industry, organotin compounds
are utilized for esterification and transesterification reac-
tions, for silicone curing, for the preparation of polyure-
thanes [15], but the stabilization of poly(vinyl chloride)
(PVC) is their largest application so far [16]. Organotin
have been known for their excellent biocidal properties
and they are used in agricultural biocides and additives
for antifouling paints for marine transport vessels [17]. In
the investigation of the possible utility of triorganotin tri-
chloroacetates as CX2 transfer agents it was found that
they decompose with carbon dioxide evolution in the pres-
ence of an olefin [18].
Organotin compounds occupy an important place in
academic research, as well as in industrial chemistry; they
are of interest in view of the considerable structural diver-
sity that they possess. This aspect has been attracting the
attention of a number of researchers and a multitude of
structural types have been discovered [1–3]. Many organo-
tin compounds have been tested for their in vitro activity
against a large variety of tumor lines [4–6]. Recently
organotin compounds have been used as reagents in reduc-
tion, transmetallation and coupling reactions or as extre-
mely versatile catalysts in organic reactions [7–14]; the
*
Recently, we have reported the synthesis and the spec-
troscopic characterization of new poly(pyrazolyl)borate
Corresponding author. Tel./fax: +39 (0) 737 402213.
E-mail address: maura.pellei@unicam.it (M. Pellei).
0022-328X/$ - see front matter Ó 2007 Elsevier B.V. All rights reserved.
doi:10.1016/j.jorganchem.2007.12.021

M. Pellei et al. / Journal of Organometallic Chemistry 693 (2008) 996–1004
997
[19,20] and poly(imidazolyl)borate [21,22] complexes con-
taining organotin(IV) acceptors. It has been our endeavor
to develop the chemistry of organotin compounds bearing
co-ligands of ambidentate character. The primary impetus
has been to comprehend competitive coordination modes
of poly(azolyl)borate ligands to the tin atom and find a
rationale related to the stability and structural motifs of
this class of compounds [23]. As an extension of this
research field, we have developed the chemistry of some
new organotin carboxylates obtained by the interaction
of a number of organotin(IV) halides with new polyfunc-
tional S,N,O-ligands, containing two pyridine groups and
other biologically relevant hydrophilic moieties, such as
carboxylate groups [24].
In recent years, a number of authors [25–34] have syn-
thesized S,N-ligands of the type (CH2)n(SAz)2 based on a
nitrogenated aromatic ring system such as benzimidazole
or pyridine. These ligands are able to coordinate by both
S and the neighbouring N atom, and hence to form stable
chelate rings of five or more atoms [35–41]. In particular,
Gardinier [42,43] and Casas [44] have recently reported
the synthesis, the analytic, spectroscopic and structural
characterization of the bis(thioimidazolyl)methane family
of compounds. These compounds are attractive owing to
both their potential biomedical applications [45,46] and
their potential utility in fundamental coordination chemis-
try [44,47–51].
Bearing in mind the above, we have developed a strategy
for producing a new class of monoanionic and polyfunc-
tional N,O,S-ligands of possible considerable coordinative
flexibility. Towards this end, we report now the synthesis
and characterization of the new sodium bis(1-methyl-
1H-imidazol-2-ylthio)acetate ligand, Na[(S-tim)2CHCO2]
(Fig. 1) and its interaction with a number of di- and tri-
organotin(IV) halides. Complexes of the type {[j1O-(S-
tim)2CHCO2]SnR3} and related decarboxylated species
{[j2N,N-(S-tim)2CH2]SnR2Cl2} have been obtained and
characterized. Since carboxylic acid derivatives are ubiqui-
tous synthetic building blocks, the ability to access reactive
organometallic species via decarboxylation offers clear
practical advantages [52–56].
Schlenk techniques or a glove box. All solvents were dried,
degassed and distilled prior to use. Elemental analyses
(C,H,N,S) were performed in house with a Fisons Instru-
ments 1108 CHNS-O Elemental Analyser. Melting points
were taken on an SMP3 Stuart Scientific Instrument. Ther-
mal Analysis was performed using a power compensation
Differential Scanning Calorimeter (DSC Pyris1, Perkin–
Elmer US Instrument Division, Norwalk, CT 06859
USA); the instrument was previously calibrated for melting
enthalpy and temperature using high grade purity Indium
as a standard. IR spectra were recorded from 4000 to
100 cmꢀ1 with a Perkin–Elmer System 2000 FT-IR instru-
ment. IR annotations used: br = broad, m = medium,
mbr = medium broad, s = strong, sbr = strong broad,
1
sh = shoulder, w = weak. H, 13C and 119Sn NMR spectra
were recorded on a Oxford-400 Varian spectrometer
1
(400.4 MHz for H, 100.1 MHz for 13C and 149.3 MHz
for 119Sn). NMR annotations used: m = multiplet, s = sin-
glet. Electrospray mass spectra (ESIMS) were obtained in
positive- or negative-ion mode on a Series 1100 MSD
detector HP spectrometer, using an acetone mobile phase.
The compounds were added to the reagent grade methanol
to give solutions of approximate concentration 0.1 mM.
These solutions were injected (1 lL) into the spectrometer
via a HPLC HP 1090 Series II fitted with an autosampler.
The pump delivered the solutions to the mass spectrometer
source at a flow rate of 300 lL minꢀ1, and nitrogen was
employed both as a drying and nebulizing gas. Capillary
voltages were typically 4000 V and 3500 V for the positive-
and negative-ion mode, respectively. Confirmation of all
major species in this ESIMS study was aided by compari-
son of the observed and predicted isotope distribution pat-
terns, the latter calculated using the ISOPRO 3.0 computer
program.
3. Experimental
3.1. Synthesis
3.1.1. Na[(S-tim)2CHCO2] (1)
2-Mercapto-1-methylimidazole (5.000 g, 43.8 mmol) was
added to a solution of NaOH (4.380 g, 109.5 mmol) in
100 mL of absolute ethanol. After 12 h stirring, a solution
of dibromoacetic acid (4.770 g, 21.9 mmol) in 40 mL of
absolute ethanol was added dropwise to the sodium salt
so obtained, and this mixture was stirred at gentle reflux
for 6 h to give an orange emulsion. The mixture was
allowed to cool to rt, filtered and then concentrated
2. Materials and methods
2.1. General procedures
All syntheses and handling were carried out under an
atmosphere of dry oxygen-free dinitrogen, using standard
Fig. 1. Synthesis of the sodium bis(1-methyl-1H-imidazol-2-ylthio)acetate ligand, Na[(S-tim)2CHCO2], starting from 2-mercapto-1-methylimidazole.
Conditions: (i) NaOH in ethanol solution, r.t., 12 h; (ii) dibromoacetic acid, reflux, 6 h.

998
M. Pellei et al. / Journal of Organometallic Chemistry 693 (2008) 996–1004
affording an orange/yellow solid. The crude product was
re-crystallized from chloroform/petroleum ether (1:4),
yielding Na[(S-tim)2CHCO2] (1) as microcrystalline nee-
(major positive-ions, CH3OH), m/z (%): 241 (80) [(S-
tim)2CHCO2 ꢀ CO2 + 2H]+, 634 (100) [{[(S-tim)2CHCO2]
Sn(C6H5)3} + H]+. ESIMS (major negative-ions, CH3OH),
m/z (%): 421 (100) [Sn(C6H5)3Cl + Cl]ꢀ. Calc. for
C28H26N4O2S2Sn: C, 53.10; H, 4.14; N, 8.85; S, 10.13.
Found: C, 52.90; H, 4.28; N, 8.69; S, 9.80%. The dichloro-
methane reaction solution of 2 was re-crystallized and the
decarboxylated species {[(S-tim)2CH2]SnCl(H2O)(C6H5)3}
(5) was obtained as a crystalline solid and characterized
by X-ray crystallography.
1
dles. Yield 75%. Mp. 110–120 °C dec. H NMR (CDCl3,
293 K): d 3.52 (s, 6H, CH3), 5.05 (s, 1H, CHCOO), 6.90
1
(s, 2H, CH), 6.97 (s, 2H, CH). H NMR (D2O, 293 K):
d 3.47 (s, 6H, CH3), 4.73 (s, 1H, CHCOO), 6.85 (d, 2H,
CH), 6.99 (d, 2H, CH). 1H NMR (D2O/DCl, 293 K):
d 3.45 (s, 6H, CH3), 6.84 (d, 2H, CH), 6.97 (d, 2H, CH).
1H NMR (CD3OD, 293 K): d 3.75 (s, 6H, CH3), 4.89 (s,
1H, CHCOO), 6.96 (d, 2H, CH), 7.15 (d, 2H, CH). 13C
NMR (CDCl3, 293 K): d 34.10 (CH3), 62.23 (CHCOO),
123.42 (CH), 129.97 (CH), 139.88 (CS), 173.14 (CHCOO).
13C NMR (D2O, 293 K): d 33.72 (CH3), 60.79 (CHCOO),
125.14 (CH), 128.94 (CH), 137.80 (CS), 173.30 (CHCOO).
13C NMR (D2O/DCl, 293 K): d 33.71 (CH3), 60.52
(CHCOO), 125.13 (CH), 128.94 (CH), 137.79 (CS),
173.27 (CHCOO). IR (Nujol, cmꢀ1): 3091w (CH),
1615sbr (masymC@O), 1506m (C@C + C@N), 1350sh
(msymC@O), 686s, 667m, 627w, 505s, 422sbr, 366m, 323w,
294m, 279w. ESIMS (major positive-ions, CH3OH), m/z
(%): 307 (100) [(S-tim)2CHCO2 + Na + H]+, 329 (80)
[(S-tim)2CHCO2 + 2Na]+, 636 (45) [{(S-tim)2CHCO2}2 +
3Na]+, 942 (30) [{(S-tim)2CHCO2}3 + 4Na]+, 1248 (10)
[{(S-tim)2CHCO2}4 + 5Na]+. ESIMS (major negative-
ions, CH3OH), m/z (%): 239 (100) [(S-tim)2CHCO2 ꢀ
CO2]ꢀ, 283 (30) [(S-tim)2CHCO2]ꢀ. ESIMS (major
positive-ions, H2O), m/z (%): 241 (15) [[(S-tim)2CHCO2] ꢀ
CO2 + 2H]+, 285 (40) [(S-tim)2CHCO2 + 2H]+, 307 (100)
[(S-tim)2CHCO2 + Na + H]+, 329 (15) [(S-tim)2CHCO2 +
2Na]+, 636 (20) [{(S-tim)2CHCO2}2 + 3Na]+, 942 (20)
[{(S-tim)2CHCO2}3 + 4Na]+. ESIMS (major negative-
ions, H2O), m/z (%): 239 (100) [(S-tim)2CHCO2 ꢀ
CO2]ꢀ, 283 (25) [(S-tim)2CHCO2]ꢀ. ESIMS (major posi-
tive-ions, H2O/CH3COOH), m/z (%): 241 (10) [[(S-
tim)2CHCO2] ꢀ CO2 + 2H]+, 285 (100) [(S-tim)2CH-
CO2 + 2H]+, 307 (20) [(S-tim)2CHCO2 + Na + H]+.
ESIMS (major negative-ions, H2O/CH3COOH), m/z
(%): 239 (100) [(S-tim)2CHCO2 ꢀ CO2]ꢀ, 283 (30) [(S-
tim)2CHCO2]ꢀ. Calc. for C10H11N4NaO2S2: C, 39.21; H,
3.62; N, 18.29; S, 20.93. Found: C, 39.04; H, 3.81; N,
18.03; S, 20.67%.
3.1.3. {[j1O-(S-tim)2CHCO2]Sn(C4H9)3} (3)
Complex 3 was prepared analogously to compound 2 by
using (C4H9)3SnCl (0.325 g, 1.0 mmol) and Na[(S-tim)2-
CHCO2] (0.306 g, 1.0 mmol) in chloroform solution
(50 mL). The yellow product was re-crystallized from chlo-
1
roform/n-hexane (1/3), in 85% yield. H NMR (CDCl3,
293 K): d 0.85–1.58 (m, 27H, Sn C4H9), 3.67 (s, 6H,
CH3), 5.34 (s, 1H, CHCOO), 6.92 (s, 2H, CH), 7.04 (s,
2H, CH). 119Sn NMR (CDCl3, 293 K): 127.96 (s). IR
(Nujol, cmꢀ1): 3136w, 3106w (CH), 1642s (masymC@O),
1511m (C@C + C@N), 1335m (msymC@O), 573s (Sn–C),
455s (Sn–O). ESIMS (major positive-ions, CH3OH), m/z
(%): 574 (100) [{[(S-tim)2CHCO2]Sn(C4H9)3} + H]+, 863
(30) [{[(S-tim)2CHCO2][Sn(C4H9)3]2}]+. ESIMS (major
negative-ions, CH3OH), m/z (%): 379 (100) [Sn(C4H9)3-
Cl(H2O) + Cl]ꢀ, 239 (40) [(S-tim)2CH]ꢀ, 857 (40) [{[(S-
tim)2CHCO2]2[Sn(C4H9)3]}]ꢀ. Calc. for C22H38N4O2S2Sn:
C, 46.08; H, 6.68; N, 9.77; S, 11.18. Found: C, 45.89; H,
6.82; N, 9.59; S, 10.98%. Re-crystallization of the crude
product from chloroform/diethyl ether (1:1) gave the
species {[j1O-(S-tim)2CHCO2]Sn(H2O)(C4H9)3} (3 ꢁ H2O)
as a crystalline solid suitable for X-ray crystallographic
study.
3.1.4. {[j1O-(S-tim)2CHCO2]Sn(C6H11)3} (4)
Compound 4 was prepared analogously to compound 2,
by using (C6H11)3SnCl (0.404 g, 1.0 mmol) and Na[(S-
tim)2CHCO2] (0.306 g, 1.0 mmol) in chloroform solution
(50 mL). The product was re-crystallized from chloro-
1
form/n-hexane. Yield: 55%. H NMR (CDCl3, 293 K): d
1.32–1.93 (m, 33H, Sn–C6H11), 3.70 (s, 6H, CH3), 5.42 (s,
119
3.1.2. {[j1O-(S-tim)2CHCO2]Sn(C6H5)3} (2)
1H, CHCOO), 6.93 (s, 2H, CH), 7.06 (s, 2H, CH).
Sn
NMR (CDCl3, 293 K): 37.76 (s). IR (Nujol, cmꢀ1):
3136w (CH), 1639s (masymC@O), 1511m (C@C + C@N),
1328s (msymC@O), 603s; 505m (Sn–C), 420mbr (Sn–O),
336m, 325s, 304m, 252m. ESIMS (major positive-ions,
CH3OH), m/z (%): 241 (70) [[(S-tim)2CHCO2] ꢀ CO2 +
2H]+, 285 (60) [(S-tim)2CHCO2 + 2H]+, 653 (100)
[{[(S-tim)2CHCO2]Sn(C6H11)3} + H]+. ESIMS (major
negative-ions, CH3OH), m/z (%): 239 (60) [(S-tim)2-
CHCO2 ꢀ CO2]ꢀ, 283 (10) [(S-tim)2CHCO2]ꢀ, 590 (60)
[{(S-tim)2CHCO2}2 + Na]ꢀ, 687 (100) [{[(S-tim)2CH-
CO2]2Sn(C6H11)3 + Cl}]ꢀ. Anal. Calc. for C28H44N4O2-
S2Sn: C, 51.62; H, 6.81; N, 8.60; S, 9.84. Found: C,
51.16; H, 7.01; N, 8.75; S, 10.02%.
To a chloroform solution (50 mL) of (C6H5)3SnCl
(0.385 g, 1.0 mmol), Na[(S-tim)2CHCO2] (0.306 g, 1.0 mmol)
was added at room temperature. After addition, the reac-
tion mixture was stirred for 4 h and then filtered; the sol-
vent was removed under vacuum and the residue was
washed with chloroform/n-hexane (1:5). The yellow prod-
uct was re-crystallized from chloroform/n-hexane. Yield:
1
43%. H NMR (CDCl3, 293 K): d 3.50 (s, 6H, CH3), 5.32
(s, 1H, CHCOO), 6.83 (s, 2H, CH), 7.03 (s, 2H, CH),
7.44–7.71 (m, 15H, Sn–C6H5). 119Sn NMR (CDCl3,
293 K): ꢀ95.83 (s). IR (Nujol, cmꢀ1): 3116w (CH), 1656s
(masymC@O), 1508m (C@C + C@N), 1308s (msymC@O),
456s (Ph), 444m, 429m (Sn–O), 278s, 245s (Sn–C). ESIMS

M. Pellei et al. / Journal of Organometallic Chemistry 693 (2008) 996–1004
999
3.1.5. {[j2N,N-(S-tim)2 CH2]Sn(C6H5)2 Cl2} (6)
parameters (1.2 Uequiv of the parent carbon atom). The cal-
culations were performed with the SHELXL-97 [59] program,
implemented in the WinGX package [60]. Crystallographic
and experimental details for the structure are summarized
in Table 1.
To a chloroform solution (50 mL) of (C6H5)2SnCl2
(0.344 g, 1.0 mmol), Na[(S-tim)2CHCO2] (0.306 g, 1.0 mmol)
was added at room temperature. After addition, the reac-
tion mixture was stirred for 4 h and then filtered; the sol-
vent was removed under vacuum and the residue was
washed with chloroform/n-hexane (1:5). The product was
re-crystallized from chloroform/diethyl ether (1:1), to give
the decarboxylate complex 6 in 44% yield. 1H NMR
(CDCl3, 293 K): d 3.62 (s, 6H, CH3), 4.44 (s, 2H, CH2),
6.95 (s, 2H, CH), 7.10 (s, 2H, CH), 7.44–7.88 (m, 10H,
C6H5). 119Sn NMR (CDCl3, 293 K): ꢀ200.26 (s). IR
(Nujol, cmꢀ1): 3116w, 3043w (CH), 1513m (C@C + C@N),
456s (Ph), 275s (Sn–C), 229br (Sn–Cl). ESIMS (major
positive-ions, CH3OH), m/z (%): 241 (100) [(S-tim)2CH2 +
H]+, 585 (40) [{[(S-tim)2CH2]Sn(C6H5)2Cl2} + H]+. ESIMS
(major negative-ions, CH3OH), m/z (%): 379 (100)
[(C6H5)2SnCl2 + Cl]ꢀ. Calc. for C21H22Cl2N4S2Sn: C,
43.18; H, 3.80; N, 9.59; S, 10.98. Found: C, 42.97; H,
3.78; N, 9.23; S, 10.63%.
4. Results and discussion
4.1. Synthesis
The sodium salt of bis(1-methyl-1H-imidazol-2-
ylthio)acetate, 1, has been prepared in absolute ethanol
solution using 2-mercapto-1-methylimidazole, dibromoace-
tic acid and sodium hydroxide by the multiple routes as
summarized in Fig. 1. While it has been reported that 2-
mercapto-1-methylimidazole exists as predominantly the
NH rather than SH tautomer in solution, [43] the greater
acidity of the thiol moiety results in the formation of thio-
late species on reaction with Brønsted bases. Compound 1
is an air-stable orange/yellow semi-crystalline solid; it is
soluble in methanol, water, acetonitrile, and chlorinated
solvents. The ligand Na[(S-tim)2CHCO2] was analysed by
Thermal Analysis at 2 °C/min and 10 °C/min in a range
of temperature between 20 °C and 130 °C; then heating/
cooling/heating cycle at 10, 30 and 50 °C was performed
between ꢀ45 °C and 90 °C. Results show a degradation
at around 110–120 °C, without loss of mass detected before
the degradation.
3.1.6. {[j2N,N-(S-tim)2 CH2]Sn(C4H9)2Cl2} (7)
Complex 7 was prepared analogously to compound 6 by
using (C4H9)2SnCl2 (0.304 g, 1.0 mmol) and Na[(S-
tim)2CHCO2] (0.306 g, 1.0 mmol) in chloroform solution
(50 mL). The product was re-crystallized from dichloro-
methane/n-hexane/petroleum ether, in 41% yield. Re-crys-
tallization of the crude product from dichloromethane/n-
hexane gave the complex 7 as a crystalline solid. 1H
NMR (CDCl3, 293 K): d 0.90–1.84 (m, 18H, Sn–C4H9),
3.67 (s, 6H, CH3), 4.65 (s, 2H, CH2), 6.98 (s, 2H, CH),
7.13 (s, 2H, CH). IR (Nujol, cmꢀ1): 3111w (CH), 1512m
(C@C + C@N), 590m (Sn–C), 235br (Sn–Cl). ESIMS
(major positive-ions, CH3OH), m/z (%): 241 (100)
[(S-tim)2CH2 + H]+, 263 (20) [(S-tim)2CH2 + Na]+.
ESIMS (major negative-ions, CH3OH), m/z (%): 339
(100) [(C4H9)2SnCl2 + Cl]ꢀ, 883 (30) [{[(S-tim)2CH2]-
[Sn(C4H9)2Cl2]2} + Cl]ꢀ. Calc. for C17H30Cl2N4S2Sn: C,
37.52; H, 5.56; N, 10.30; S, 11.78. Found: C, 37.49; H,
5.52; N, 10.19; S, 11.60%.
Table 1
Experimental data for the crystallographic analyses
5
3 ꢁ H2O
Compound
{[(S-tim)2CH2]SnCl- {[j1O-(S-tim)2CHCO2]-
(H2O)(C6H5)3}
C27H29ClN4OS2Sn
643.80
Sn(H2O)(C4H9)3}
C22H38N4O3S2Sn
589.37
Empirical formula
Formula weight
Temperature (K)
293(2)
293(2)
˚
Radiation (k, A)
Mo Ka (0.71073)
Triclinic
Mo Ka (0.71073)
Monoclinic
I2/a
18.454(3)
15.761(3)
Crystal system
Space group
ꢀ
P1
˚
a (A)
10.232(2)
11.528(2)
13.474(2)
107.54(2)
108.63(3)
90.13(2)
1427.5(4)
2
1.498
652
3–28
11.62
˚
3.2. X-ray measurements and structure determination for
{[(S-tim)2CH2]SnCl(H2O)(C6H5)3} (5), {[j1O-(S-
tim)2CHCO2]Sn(H2O)(C4H9)3} (3 ꢁ H2O)
b (A)
˚
c (A)
21.945(4)
a (°)
b (°)
c (°)
110.92(3)
3
˚
The Intensities data were collected at room temperature
using Philips PW1100 diffractometer using graphite mono-
Volume (A )
5962(2)
8
Z
Dcalc (g cmꢀ3
F(000)
)
1.313
2432
3–26
10.23
6280
4099
0.051
0.143
1.040
˚
chromated Mo Ka radiation (0.71073 A), following the
standard procedures at room temperature. There were no
significant fluctuations of intensities other than those
expected from Poisson statistics. All intensities were cor-
rected for Lorentz polarization and absorption [57]. The
structures were solved by standard direct methods [58].
Refinement was carried out by full-matrix least-squares
procedures (based on F2o) using anisotropic temperature
factors for all non-hydrogen atoms. Hydrogen atoms were
placed in calculated positions with fixed, isotropic thermal
h Range (°)
l (cmꢀ1
)
No. reflections collected 7176
No. observed [I P 2r(I)] 5546
R (Fo)a
Rw (F2o)b
0.040
0.094
1.060
Goodness of fit
P
P
a
R = kFoj ꢀ jFck/ jFoj.
P
P
b
Rw = {[ w(Fo2 ꢀ F2c)2]/ [w(Fo2)2]}1/2
.

1000
M. Pellei et al. / Journal of Organometallic Chemistry 693 (2008) 996–1004
Complexes 2–4 have been synthesized by metathetic
talline solid from the crystallization by slow evaporation
reaction of Na[(S-tim)2CHCO2] with R3SnCl acceptors
(R = C6H5, C4H9 or C6H11) in chloroform solution at
room temperature (Eq. (1)).
of the reaction solution.
The derivatives {[j2N,N-(S-tim)2CH2]Sn(C6H5)2Cl2}, 6
and {[j2N,N-(S-tim)2CH2]Sn(C4H9)2Cl2}, 7, are reason-
1
CHCl /r.t.
3
Na[(S-tim)2CHCO2] + R3SnCl
[ O-(S-tim)2CHCO2]SnR3 + NaCl
2: R = C6H5
1
ð1Þ
3: R = C4H9
4: R = C6H11
The derivatives 2–4 are stable under inert atmosphere; they
show a good solubility in methanol, acetone, acetonitrile
and chlorinated solvents, and they are insoluble in water,
diethyl ether and n-hexane. Re-crystallization of the crude
product 3 from chloroform/diethyl ether (1:1) gave the
Lewis adduct with water {[j1O-(S-tim)2CHCO2]Sn(H2O)-
(C4H9)3}, 3 ꢁ H2O, as a crystalline solid suitable for X-ray
crystallographic study (Eq. (2)).
ably stable in air; they show a good solubility in methanol,
acetone, acetonitrile and chlorinated solvents, and they are
insoluble in water, diethyl ether and n-hexane. Re-crystalli-
zation of the crude product 7 from dichloromethane/n-hex-
ane gave the complex {[j2N,N-(S-tim)2CH2]Sn(C4H9)2Cl2}
(Fig. 2), as a crystalline solid. The same compound was
obtained using as starting material the neutral bis(1-
methyl-2-imidazolylthio)methane ligand, [(S-tim)2CH2],
ð2Þ
Complexes 6 and 7 have been obtained by reaction of
Na[(S-tim)2CHCO2] with R2SnCl2 acceptors (R = C6H5
or C4H9) in chloroform solution at room temperature
(Fig. 2). The decarboxylation of the ligand likely occurs
in presence of traces of moisture, that can be introduced
into the system with the reagents. In fact in water solution
the decarboxylation of the ligand occurs yielding the
[(S-tim)2CH2] species.
This may not necessarily interfere with the initial forma-
tion of the complexes, but then causes the decomposition
of the diorganotin derivatives due to their hygroscopic nat-
ure via decarboxylation of the ligand [19]. Analogously,
from the reaction of Na[(S-tim)2CHCO2] with (C6H5)3SnCl
the main product {[j1O-(S-tim)2CHCO2]Sn(C6H5)3}, 2,
was obtained together with the decarboxylated species
{[(S-tim)2CH2]SnCl(H2O)(C6H5)3}, 5, obtained as a crys-
and the crystal structure of compound 7 has been already
reported by Casas et al. [44].
4.2. Spectroscopy
The ligand 1 and the derivatives 2–6 have been charac-
terized by analytical and spectral data. Infrared spectros-
copy carried out on the solid samples (Nujol mull)
showed all the expected bands for the ligand and the tin
moieties: weak absorptions in the range 3043–3136 cmꢀ1
are due to the azolyl ring C–H stretchings and medium
to strong absorptions near 1510 cmꢀ1 are related to ring
‘‘breathing” vibrations. The presence of the COO moiety
in derivatives 2–4 is detected by an intense broad absorp-
tion in the range 1639–1656 cmꢀ1 and 1308–1335 cmꢀ1
due to the asymmetric and symmetric stretching modes,
,
Fig. 2. Proposed synthesis of the diorganotin(IV) derivatives 6 and 7, {[j2N,N-(S-tim)2CH2]SnR2Cl2} (R = C6H5 and C4H9).

M. Pellei et al. / Journal of Organometallic Chemistry 693 (2008) 996–1004
1001
respectively; the shift to blue with respect to the sodium salt
the molecular ion plus some adduct ion from the mobile
phase solutions [68,69]. ESIMS is particularly suitable for
study of labile organotin systems in solution. In the discus-
sion of the mass spectra of the ligand and the di- and tri-
organotin(IV) derivatives, only the most abundant ion of
the isotope cluster will be mentioned. In the positive-ion
spectrum of the ligand 1, dissolved in methanol solution
and detected at fragmentation voltage of 30V, significant
fragments at m/z 307 (100%), m/z 329 (80%), m/z 636
(45%), m/z 942 (30%) and m/z 1248 (10%) have been
attributable to the species [(S-tim)2CHCO2 + Na + H]+,
[(S-tim)2CHCO2 + 2Na]+, [{(S-tim)2CHCO2}2 + 3Na]+,
[{(S-tim)2CHCO2}3 + 4Na]+ and [{(S-tim)2CHCO2}4 +
5Na]+, respectively. In the negative-ion spectrum a
fragment at m/z 283 (20%) is due to the free ligand
[(S-tim)2CHCO2]ꢀ and of a major peak at m/z 239
(100%) is attributable to the decarboxylated specie
[(S-tim)2CHCO2 ꢀ CO2]ꢀ. A similar pattern has been
observed in the positive- and negative-ion spectra of the
ligand 1, dissolved in water or water/acetic acid solution.
In the positive-ion spectra of the triorganotin(IV) deriv-
atives 2–4 significant fragments at m/z 634 (100%), 574
(100%) and 653 (100%) have been attributable to the com-
plexes [{[(S-tim)2CHCO2]SnR3} + H]+. The instability of
the triorganotin(IV) derivatives in methanol solution is
demonstrated by the presence in the positive- and nega-
tive-ion spectra of fragments at m/z 241 and m/z 239 due
to the decarboxylated ligand, [(S-tim)2CHCO2 ꢀ CO2 +
2H]+ and [(S-tim)2CHCO2 ꢀ CO2]ꢀ, respectively; more-
over in the negative-ion spectra the main fragments at m/
z 421 (100%) and m/z 379 (100%) have been attributable
to the free organotin(IV) acceptors [{Sn(C6H5)3Cl} + Cl]ꢀ
and [Sn(C4H9)3Cl(H2O) + Cl]ꢀ. In the positive- and nega-
tive-ion spectra of the diorganotin(IV) derivatives 6 and 7
the main fragments have been attributable to the free
ligand [(S-tim)2CH2 + H]ꢀ at m/z 241 (100%) and to the
free organotin acceptors [(C6H5)2SnCl2 + Cl]ꢀ and
[(C4H9)2SnCl2 + Cl]ꢀ, at m/z 379 (100%) and m/z 339
(100%), respectively.
of the ligand (masymC@O = 1615 cmꢀ1), being observed
upon complex formation. The magnitude of masym
-
CO2 ꢀ msymCO2 (Dm) separation can be used to explain
the type of carboxylate structure present in the solid state
[61,62]. Dm values for 2–4 are of about 300 cmꢀ1, character-
istic of monodentate coordination compounds. The
absence of strong absorptions in the range at 1600–
1700 cmꢀ1 in the IR spectra of derivatives 6 and 7 confirms
the decarboxylation of the ligand in these complexes. In the
far-IR region medium to strong absorptions appear upon
coordination, due to stretching modes of Sn–O, Sn–Cl,
Sn–C [63]. The absence of Sn–Cl stretching vibrations in
the spectra of the triorganotin(IV) derivatives 2–4 confirms
the substitution of the chloride in the complexes formation.
The Sn–Cl stretching vibrations fall as broad absorptions
near 229–235 cmꢀ1 in the diorganotin(IV) derivatives 6
and 7. The Sn–C stretching frequencies fall as medium or
strong absorptions in the range 245–275 cmꢀ1 for the aryl
derivatives 2 and 6; similar stretching vibrations are
detected in the range 505–590 cmꢀ1 for the alkyl derivatives
3, 4 and 7. These absorptions agree well with the trends
previously observed in similar N-donor complexes [64].
In the far-IR spectra absorptions tentatively assigned to
Sn–O have been detected in the range 420–455 cmꢀ1 in
the triorganotin(IV) derivatives.
1
The H and 13C NMR spectra of a CDCl3, D2O and
D2O/DCl solution of Na[(S-tim)2CHCO2], 1, agrees with
the proposed formula. It is important to note that the res-
onance for CHCOO group hydrogens occurs at 5.05 and
4.73 ppm, in CDCl3 and D2O solution, respectively, down-
field with respect to the decarboxylate analogues
1
[(S-tim)2CH2] [44]. In the H NMR spectra of complexes
2–6, in CDCl3 solution (see Section 3), the signals due to
the 2-mercapto-1-methylimidazolyl rings are always
deshielded with respect to those in the spectra of the free
donor, confirming the existence of the complexes in solu-
tion; the signals due to the CHCOO group exhibit signifi-
cant downfield shift (from 5.05 ppm in the free ligand to
5.32–5.42 ppm in the complexes 2–4): this is suggestive of
a strong bonding of the tin atom to the carboxylate group
of the complexes. In the 1H NMR spectra at room temper-
ature of the decarboxylated derivatives 6 and 7, the
resonances due to the bridging methylene protons of the
[(S-tim)2CH2] ligand appear as singlets at 4.44 and
4.65 ppm, respectively, probably as a result of averaging
arising from rapid ring inversion of the puckered eight-
membered ring containing the central Sn atom.
4.3. X-ray crystallography
The ORTEP representation and the numbering scheme
of the complexes {[(S-tim)2CH2]SnCl(H2O)(C6H5)3}, 5,
and {[j1O-(S-tim)2CHCO2]Sn(H2O)(C4H9)3}, 3 ꢁ H2O,
are shown in Figs. 3 and 4; selected bond lengths and
angles are listed in Table 2.
Several structures of (C6H5)3SnCl(H2O) co-crystallized
with other molecules have been determined, for example
3-[2-(1,10-phenanthrolyl)]-5,6-diphenyl-1,2,4-triazine [70],
3,4,7,8-tetramethyl-1,10-phenanthroline [71], [N,N0-bis-(3-
methoxysalicylidene)propane-1,3-diamine]nickel(II) [72],
di-2-pyridylketone 2-aminobenzoylhydrazone [73], o-phe-
nanthroline [71], 2,20:60,200-terpyridyl [74], 18-crown-6
[75], 8-methoxyquinoline [76], di-2-pyridyl-2-thenoylhyd-
razone [77] and pyridine [78]. In these structures, there is
hydrogen bonding between the coordinated water molecule
1
The room temperature H NMR spectra of derivatives
2–6 exhibit only one set of signals for the protons of the
imidazolyl rings of the ligands. The 119Sn chemical shifts
of the triorganotin(IV) derivatives 2–4, at ꢀ95.83, 127.96
and 37.76 ppm, respectively, are in accordance with those
of penta-coordinate triorganotin(IV)complexes involving
S-, O- or N-donors [65–67].
Electrospray ionization is considered a ‘soft’ ionization
technique. Consequently, few ions are produced, usually

1002
M. Pellei et al. / Journal of Organometallic Chemistry 693 (2008) 996–1004
Fig. 3. View of the structure of {[(S-tim)2CH2]SnCl(H2O)(C6H5)3}, 5, showing the hydrogen bonding between the coordinated water molecule of
(C6H5)3SnCl(H2O) and the atoms of (S-tim)2CH2 co-crystallized molecules in the structure (at 1 ꢀ x, 1 ꢀ y, ꢀz).
Table 2
˚
Selected bond lengths (A) and angles (°) for compounds 5 and 3 ꢁ H2O
Compound 5
Sn–Cl
Sn–C(7)
2.538(1)
2.130(4)
2.147(4)
1.797(4)
1.821(4)
1.356(4)
1.319(5)
1.350(4)
1.465(6)
1.372(6)
Sn–O
Sn–C(1)
2.351(3)
2.132(4)
1.758(4)
1.744(4)
1.350(6)
1.459(6)
1.369(5)
1.368(5)
1.320(5)
Sn–C(13)
S(2)–C(19)
S(1)–C(19)
N(1)–C(20)
N(2)–C(20)
N(3)–C(24)
N(3)–C(27)
N(4)–C(26)
S(2)–C(24)
S(1)–C(20)
N(1)–C(21)
N(1)–C(23)
N(2)–C(22)
N(3)–C(25)
N(4)–C(24)
O–Sn–Cl
C(7)–Sn–C(13)
C(7)–Sn–O
C(13)–Sn–O
C(1)–Sn–Cl
C(24)–S(2)–C(19)
S(1)–C(19)–S(2)
172.2(1)
113.9(1)
85.0(1)
89.5(1)
91.1(1)
99.0(2)
112.0(2)
C(7)–Sn–C(1)
C(1)–Sn–C(13)
C(1)–Sn–O
C(7)–Sn–Cl
C(13)–Sn–Cl
C(20)–S(1)–C(19)
121.3(2)
124.0 (2)
85.7(1)
90.6(1)
98.1(1)
102.6(2)
Fig. 4. The molecular structure of {[j1O-(S-tim)2CHCO2]Sn(H2O)-
(C4H9)3}, 3 ꢁ H2O.
Compound 3 ꢁ H2O
Sn–O(1)
Sn–C(11)
Sn–C(19)
S(1)–C(2)
2.386(4)
2.144(6)
2.139(5)
1.807(4)
1.824(6)
Sn–O(2)
2.196(4)
2.111(6)
1.529(6)
1.746(6)
1.755(7)
Sn–C(15)
C(1)–C(2)
S(1)–C(3)
S(2)–C(7)
of (C6H5)3SnCl(H2O) and the N2 and N4 nitrogen atoms
of co-crystallized molecules in the structure. In this paper,
we report a structure in which the bis(1-methyl-1H-imida-
zol-2-ylthio)methane species is hydrogen bonded to
Ph3SnCl(H2O) (Fig. 3). In the molecular structure of com-
pound 5, the tin atom is five-coordinated in a slightly dis-
torted trigonal-bipyramidal geometry by three carbon
atoms of three phenyl groups in the equatorial plane, and
by one chlorine anion and one water molecule in the axial
positions. The slight distortion from the ideal trigonal-
bipyramidal geometry is reflected in the O–Sn–Cl angle
of 172.2(1)°, and the three C–Sn–C angles of 121.3(2)°,
113.9(1)° and 124.0(2)°. The two thioimidazolyl moieties
are connected to the coordinated water molecule through
O–Hꢁ ꢁ ꢁN hydrogen bonds. The O–H(1)ꢁ ꢁ ꢁN(2) and
O–H(2)ꢁ ꢁ ꢁN(4)0 (at 1 ꢀ x, 1 ꢀ y, ꢀz) contact distances are
S(2)–C(2)
O(1)–Sn–O(2)
C(11)–Sn–C(19)
C(11)–Sn–O(1)
C(19)–Sn–O(1)
C(15)–Sn–O(2)
C(2)–S(1)–C(3)
S(1)–C(2)–S(2)
C(1)–C(2)–S(2)
177.4(2)
117.3(4)
87.1(3)
84.2(2)
94.9(3)
101.1(3)
107.6(3)
112.0(3)
C(11)–Sn–C(15)
C(15)–Sn–C(19)
C(15)–Sn–O(1)
C(11)–Sn–O(2)
C(19)–Sn–O(2)
C(2)–S(2)–C(7)
C(1)–C(2)–S(1)
118.1(4)
123.4(3)
87.5(3)
90.8(3)
95.4(2)
100.5(3)
110.6(3)
˚
˚
1.65(6) A and 1.92(5) A, with angles of 172° and 175°,
respectively. These values are comparable to those found
in similar pyridine ligand adducts [78].
X-ray quality crystals of 3 ꢁ H2O were obtained from a
CHCl3/diethyl ether (1:2) solution. The structure consists

M. Pellei et al. / Journal of Organometallic Chemistry 693 (2008) 996–1004
1003
of discrete {[j1O-(S-tim)2CHCO2]Sn(H2O)(C4H9)3]} mole-
Acknowledgements
cules and the labeling for the atoms are shown in Fig. 4.
The tin atom is five-coordinated, being bonded to two oxy-
gen atoms and three butyl groups, respectively. The
coordination sphere is distorted trigonal bipyramid with
the three equatorial positions being taken up by the
carbon of the n-butyl substituents and the axial positions
being occupied by an oxygen atom of a monodentate car-
boxylate ligand and a water molecule (O(1)–Sn–O(2)
177.4(2)°). The Sn–O(2)(carboxylate) bond distance is
This work was supported by University of Camerino
(FAR) and Regione Marche, Italy (CIPE 2004).
Appendix A. Supplementary material
CCDC 660930 and 660931 contain the supplementary
crystallographic data for 5 and 3 ꢁ H2O. These data can
be obtained free of charge from The Cambridge Crystallo-
graphic Data Centre via www.ccdc.cam.ac.uk/data_
request/cif. Supplementary data associated with this article
can be found, in the online version, at doi:10.1016/
j.jorganchem.2007.12.021.
˚
significantly shorter (2.196(4) A) compared with the
˚
Sn–O(1)(water) (2.386(4) A), thus the R–CO2 moiety does
not function as a symmetric bridging ligand. Because of
the variation of the bond distances the tin atom is
˚
0.15(1) A out of the equatorial plane towards the more
strongly bound O(2) atom. The O(3) oxygen atom of the
carboxylic residue does not significantly interact with the
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