Highly Versatile Synthesis of Some Organotin(IV) Complexes of 2-Hydroxyacetophenone Semicarbazone and Thiosemicarbazone

Article abstract of DOI:10.1081/SIM-120026555

Some di- and triorganotin(IV) complexes of 2-hydroxyacetophenone semicarbazone (H₂MeSSC) and thiosemicarbazone (H₂MeSTSC) have been synthesized by the reactions of corresponding di- and triorganotin(IV) chlorides with the anionic for

Full text of DOI:10.1081/SIM-120026555

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Highly Versatile Synthesis of Some Organotin(IV)
Complexes of 2‐Hydroxyacetophenone Semicarbazone
and Thiosemicarbazone
a
a
M. S. Singh & P. K. Singh
a
Department of Chemistry , D.D.U. Gorakhpur University , Gorakhpur, 273 009 (U.P.), India
Published online: 15 Feb 2007.
To cite this article: M. S. Singh & P. K. Singh (2003) Highly Versatile Synthesis of Some Organotin(IV) Complexes of
‐Hydroxyacetophenone Semicarbazone and Thiosemicarbazone, Synthesis and Reactivity in Inorganic and Metal-Organic
2
Chemistry, 33:10, 1895-1909, DOI: 10.1081/SIM-120026555
To link to this article: http://dx.doi.org/10.1081/SIM-120026555
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SYNTHESIS AND REACTIVITY IN INORGANIC AND METAL-ORGANIC CHEMISTRY
Vol. 33, No. 10, pp. 1895–1909, 2003
Highly Versatile Synthesis of Some Organotin(IV)
Complexes of 2-Hydroxyacetophenone
Semicarbazone and Thiosemicarbazone
*
M. S. Singh and P. K. Singh
Department of Chemistry, D.D.U. Gorakhpur University,
Gorakhpur, India
ABSTRACT
Some di- and triorganotin(IV) complexes of 2-hydroxyacetophenone
semicarbazone (H MeSSC) and thiosemicarbazone (H MeSTSC) have
2
2
been synthesized by the reactions of corresponding di- and triorgano-
tin(IV) chlorides with the anionic form of the ligands in desired molar
ratios. All the compounds have been characterized by elemental analyses
1
13
119
and spectral (IR, H, C and Sn NMR) studies.
Key Words: Organotin(IV) complexes; 2-Hydroxyacetophenone
semicarbazone; Thiosemicarbazone; Spectral studies; Dianion.
*
Correspondence: M. S. Singh, Department of Chemistry, D.D.U. Gorakhpur
University, Gorakhpur 273 009 (U.P.), India; E-mail: singhms1960@rediffmail.com.
1
895
DOI: 10.1081/SIM-120026555
0094-5714 (Print); 1532-2440 (Online)
www.dekker.com
Copyright D 2003 by Marcel Dekker, Inc.

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Singh and Singh
INTRODUCTION
The chemistry of organotin compounds recently has developed not only
[
1]
[2,5]
as reagents but also as intermediates in organic synthesis.
carbazones and thiosemicarbazones are versatile ligands in both neutral and
Semi-
[
6,7]
anionic forms.
Chelates of organotin(IV) moieties with N, O and S
have received much attention during the last few years.
Certain penta-coordinated and hexa-coordinated organotin(IV) com-
[
8–13]
donor ligands
[
14]
[15,16]
plexes,
thiosemicarbazones
a number of oximates
[
and complexes of isatin 3- and 2-
17]
have been reported in the literature having interest-
An overview of the development of antitumour
organotin derivatives has been presented and discussed for selected classes
[
18,19]
ing stereochemistry.
[
20]
of compounds.
Organotin compounds having the general formulae
[21–25]
R SnX are almost biologically active. The nature of the alkyl
group is of prime importance in determining their toxicity towards par-
ticular living species.
semicarbazones and thiosemicarbazones.
and biological importance of organotin(IV) compounds and in continuation
n
4 À n
[
26]
A recent review deals with metal complexes of
[27]
Thus, in view of the synthetic
[28–38]
of our recent report on organotin(IV),
we report herein the synthesis
and characterization of some new organotin(IV) derivatives of 2-hydro-
xyacetophenone semicarbazone and thiosemicarbazone (Figure 1).
EXPERIMENTAL
All reactions were carried out under argon atmosphere and analytical
grade chemicals were used. Solvents were purified and dried according to
[
39,40]
standard procedures.
All melting points are uncorrected. The progress
of reactions was monitored by TLC on silica gel. Elemental analyses were
performed by the Central Drug Research Institute, Lucknow. Tin in the
[
41]
complexes was determined by a gravimetric method.
recorded on a Perkin–Elmer model 377 spectrometer in the range 4000–
2
IR spectra were
–
00 cm . The H and C NMR spectra were recorded at 270.13 and 67.93
1
1
13
Figure 1. Structure of the ligands.

Organotin(IV) Complexes
1897
1
19
MHz, respectively, on a Bruker AM 270 instrument. The
spectra were recorded at 186.50 MHz on a Bruker WM 500 instrument.
Sn NMR
1
Chemical shifts are quoted in ppm downfield from TMS for H and relative
1
19
to tetramethyltin for
(
Sn and referenced to residual protons of CDCl3
d = 7.24) for H NMR. The ligands were synthesized by the condensation
of 2-hydroxyacetophenone and semicarbazide/thiosemicarbazide in 1:1
1
[
26]
molar ratio.
Reaction of Triphenyltin Chloride with the Sodium Salt
of 2-Hydroxyacetophenone Semicarbazone
in 1:1 Molar Ratio
Sodium hydride (0.048 g, 2.00 mmols) and 20 mL of dry isopropanol
were placed in a 100 mL three-necked, round-bottomed flask equipped with
an efficient magnetic stirrer, an addition funnel, a condenser and two-way
balloon system. The mixture was stirred for about half an hour till a clear
solution of sodium isopropoxide was obtained. 2-Hydroxyacetophenone
semicarbazone (0.420 g, 2.00 mmols) in 25 mL of dry benzene was then
added slowly, and the mixture was refluxed. After 30 minutes a pinkish
colour was obtained which changed to light yellow after 2 h. The contents
were allowed to attain room temperature. A solution of triphenyltin(IV)
chloride (0.789 g, 2.00 mmols) in benzene (20 mL) was added dropwise.
After complete addition, the contents were refluxed further for 2 h to ensure
the completion of the reaction, during which no specific change was
observed. The mixture was then filtered to remove the NaCl formed
during the reaction. Removal of the solvent from the filtrate under reduced
pressure on a rotary evaporator gave the desired compound as yellow
solid, which was recrystallized from a benzene–petroleum ether (2:1; 40–
60°) mixture.
All other organotin(IV) derivatives of H MeSSC and H MeSTSC were
2
2
synthesized analogously as described above in the desired molar ratios
Tables 1 and 2).
(
RESULTS AND DISCUSSION
Triorganotin(IV) and diorganotin(IV) derivatives of 2-hydroxyaceto-
phenone semicarbazone and thiosemicarbazone have been synthesized by
the reaction of corresponding tri- or diorganotin(IV) chlorides with the
sodium salt of the ligand (prepared in situ) in the desired molar ratios in
Eqs. 1 and 2.

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Singh and Singh

Organotin(IV) Complexes
1899

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Singh and Singh
Eqs. 1 and 2 show the initial formation of the monoanion and dianion
which attack the corresponding tri- and diorganotin(IV) chlorides leading to
the formation of the desired compounds. The weight of the recovered salt is
consistent with the various stoichiometric ratios of the reactions. All of
these compounds are soluble in common organic and coordinating solvents
e.g. C H , CH Cl CHCl , THF, DMF and DMSO etc.
6
6
2
2
3
Infrared Spectra
The IR spectra of the complexes have been compared with the ligand
and from the shifts in frequency and/or from the intensity lowering, the
coordination sites have been ascertained. The IR spectrum of the ligand
–
1
shows bands in the region 3496, 3442–3244, 1615 and 1024 cm
assignable to n(N–OH), n(NH ), n(C=N) and n(C=S), respectively. The
2
–
strong bands observed at 3442, 3276 and 3244 cm in all the complexes
1
rule out coordination of the NH group to the metal. The presence of OH
2
vibrations in all the complexes derived from the monoanion by Eq. 1 shows
that the phenolic OH group is non-ionized and uncoordinated, whereas in
complexes derived from the dianion by Eq. 2, the OH bands are absent
indicating deprotonation and metallation of both the phenolic and enolic

Organotin(IV) Complexes
1901
OH groups. This view is corroborated by the appearance of new bands in the
[28–31,41]
Bands
–
region 585–568 cm , ascribable to the (Sn–O) vibration.
1
due n(C=O) and n(C=S) modes in the ligands are observed at 1686 and
–
024 cm , respectively. These disappear in the spectra of the complexes
1
1
suggesting thereby enolization
[
14]
of the ligands and their chelation through
enolic oxygen or thiolic sulfur. Further, some new bands observed in the
–
1
far-IR region of the metal complexes at ꢀ 575, 415 and 360 cm are
[
28,29]
[30,31]
[10,11]
assigned to n(Sn–O),
respectively (Tables 3 and 4).
One strong band in both ligands at 1600 ± 10 cm due to n(C=N) is
n(Sn–N)
and n(Sn–S)
modes,
–
1
–
1
–1
split into two sharp bands at 1620 ± 10 cm and 1585 cm on complex
–
1
formation. The band at 1620 ± 10 cm in the metal complexes indicates
the cordination of the azomethine nitrogen to the tin atom, whereas the
other one is due to an uncoordinated azomethine group.
1
H NMR Spectra
1
The H NMR spectra of the complexes exhibit the usual features. The
signal due to phenolic OH of the ligands that appears around 11.45 ppm is
found at almost the same position in all the compounds derived from the
monoanion (Eq. 1) and is absent in the spectra of complexes derived from
the dianion (Eq. 2) showing deprotonation of both phenolic and enolic OH
groups. The presence of a sharp singlet in the range 5.48–5.88 ppm in all
the compounds shows that the NH2 group is intact, non-ionized and
uncoordinated. The resonance due to the phenyl moiety at 7.86–6.52 ppm
remains almost unchanged in all the complexes. The methyl protons
attached to tin appear as a sharp singlet in the region 0.92–0.78 ppm. The
resonances due to butyl tin protons are observed in the region 0.40–1.70
ppm (Tables 3 and 4). The spectral features and integrations are consistent
with the various stoichiometries and bonding sites as inferred from the
infrared spectra.
1
3
C NMR Spectra
1
3
C NMR spectra of the compounds were recorded in CDCl . The
3
number of observed carbon signals is in agreement with that expected in the
appropriate regions for the proposed structures. Aromatic carbons display
signals in the range 145.83–116.23 ppm. The amido, thioamido and
azomethine carbons appear at 198.40, 178.54 and 156.82 ppm, respectively,
in the ligand. On coordination, the resonances of the carbon atoms attached
to the C=N, OH and SH groups shift downfield, suggesting coordination of

1
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Singh and Singh

Organotin(IV) Complexes
1903

1
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Singh and Singh

Organotin(IV) Complexes
1905
Figure 2. Organotin(IV) complexes derived from (a) monoanion, (b) dianion.
C=N, OH and SH groups to the metal atom. Compounds (1), (3), (6), (9)
1
119
13
and (14) show J( Sn– C) values of 562, 598.6, 613.4, 567 and 622.2
Hz, respectively, and these are characteristic of 5-coordinate tin. Methyl
carbons appear in the region 10.46–9.56 ppm. Butyl carbons display peaks
in the region 13.26–26.77 ppm (Table 5).
1
19
Sn NMR Spectra
1
19
1
Sn NMR spectra of all compounds have been recorded and exhibit a
19
sharp Sn resonance in the region À253.9 to À182.8 ppm which is com-
[42,43]
patible with a penta-coordinate geometry.
CONCLUSION
Thus, on the basis of the above studies and reports already available in
the literature, the potentially bifunctional tridentate ligands 2-hydroxyace-
tophenone semicarbazone and thiosemicarbazone are only (X,N)-bidentate,
five-coordinated in a trigonal bipyramidal arrangement with N and Cl
occupying the axial positions in complexes (Figure 2a) derived from the
monoanion (Eq. 1). The ligands behave as (O,N,O) or (O,N,S)-tridentates in
the Z-configuration of a cis-trigonal bipyramidal coordination polyhedron
with the phenolic hydroxyl oxygen in one axial position and semicarba-
zonate oxygen or thiosemicarbazonate sulfur in the other (Figure 2b) in all
complexes derived from the dianion (Eq. 2).
ACKNOWLEDGMENT
Financial support from the CSIR, New Delhi is gratefully acknowledged.

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Singh and Singh
REFERENCES
1.
Mitchell, T.N. Organotin Reagents in Cross-coupling; Diederich, F.;
Stang, P.J., Eds.; Metal Catalysis Cross-coupling React, Wiley-VCH:
Weinheim, Germany, 1998; 157.
2.
Davies, A.G.; Smith, P.J. Comprehensive Organometallic Chemistry;
Wilkinson, G.; Stone, F.G.A.; Abel, E.W., Eds.; Pergamon Press:
Oxford, 1982; 579.
3.
4.
5.
Pereyre, M.; Quintard, J.P.; Rahim, A. Tin in Organic Synthesis;
Butterworth: London, 1987; 185.
Omae, I. Organotin Chemistry; J. Organomet. Chem. Library, Elsevier:
Amsterdam, 1989; Vol. 21.
Marton, D.; Russo, U.; Stivanello, D.; Tagliavini, G. Synthesis and
reactivity of hypervalent metal complexes. Organometallics 1996, 15,
1645.
6.
Casas, J.S.; Sanchez, A.; Sordo, J.; Vazquez-Lopez, A.; Castellano, E.E.;
Zukerman-Schpector, J.; Rodriguez-Arguelles, M.C. Complexes contain-
ing salicylaldehyde thiosemicarbazone. Inorg. Chim. Acta 1994, 216,
169.
Labib, L.; Khalil, J.E.; Iskander, M.F.; Refaat, L.S. Complexes con-
taining the ligand formylpyridine thiosemicarbazone. Polyhedron 1996,
15, 349.
Singh, H.L.; Varshney, A.K. Synthesis and characterization of coor-
dination compounds of organotin(IV) with nitrogen and sulfur donor
ligands. Appl. Organomet. Chem. 2001, 15, 762.
7
8
9
.
.
.
Dey, D.K.; Saha, M.K.; Das, M.K.; Bhartiya, N.; Bansal, R.K. Synthesis
and characterization of diorganotin(IV) complexes of tetradentate Schiff
bases: crystal structure of n-Bu Sn(vanophen). Polyhedron 1999, 18,
2
2687.
10. Saxena, A.; Tandon, J.P. Structural features of some organotin(IV)
complexes of semi and thiosemicarbazones. Polyhedron 1984, 3,
681.
1
1. Dey, D.K.; Saha, M.K.; Gielen, M.; Kemmer, M.; Biesemans, M.;
Willem, R. Synthesis, spectroscopy and structure of [N-(2-carboxy-
phenyl)salicylideneiminatotin(IV). J. Organomet. Chem. 1999, 590,
88.
12. Petteinari, C.; Marchetti, F.; Cingolani, A. Organotin(IV) complexes
containing mono or bidentate N-donor ligands. Polyhedron 1996, 15,
1263.
1
3. Nath, M.; Yadav, R. Spectral studies and in vitro antimicrobial activity
of new organotin(IV) complexes of Schiff bases derived from amino
acids. Bull. Chem. Soc. Jpn. 1997, 70, 1331.

Organotin(IV) Complexes
1907
1
1
1
1
4. Bhambhani, S.; Saxena, S.; Rai, A.K. A new access to penta- and hexa-
coordinated organotin(IV) complexes. Main Group Met. Chem. 1995,
8, 251.
5. Kukushkin, V.Yu.; Tudala, D.; Pombeiro, A.J.L. Metal–ion assisted
reactions of oximes and reactivity of oxime-containing metal com-
plexes. Coord. Chem. Rev. 1996, 156, 333.
6. Kukushkin, V.Yu.; Pombeiro, A.J.L. Oxime and oximate metal
complexes: unconventional synthesis and reactivity. Coord. Chem.
Rev. 1999, 181, 147.
7. Casas, J.S.; Castineiras, A.; Rodriguez-Arguelles, M.C.; Sanchez, A.;
Sordo, J.; Vazquez-Lopez, A.; Vazquez-Lopez, E.M. Reactions of
diorganotin(IV) oxides with isatin 3- and 2-thiosemicarbazones and
with isatin 3- and 2-thiosemicarbazones and with isatin 2,3-bis(thiose-
micarbazone): influence of diphenyldithiophosphinic acid. J. Chem.
Soc., Dalton Trans. 2000, 4056.
1
18. Gupta, R.K.; Rai, A.K.; Mehrotra, R.C. Reactivity and stereochemistry
of metal complexes. Inorg. Chim. Acta 1984, 82, 145.
1
9. Sharma, N.; Sharma, V.; Bhatt, S.S. Reactivity of some di- and
triphenyltin(IV) hydroxamates with ligands containing labile protons. J.
Indian Chem. Soc. 1999, 76, 469.
2
0. Gielen, M. Organotin compounds and their therapeutic potential: a
report from the organometallic chemistry department of the Free
university of Brussels. Appl. Orgamomet. Chem. 2002, 16, 481.
1. Smith, P.J. Toxicological Data on Organotin Compounds; International
Tin Research Institute: London, 1978.
2
2
2. Singh, H.L.; Varshney, S.; Varshney, A.K. Synthesis and spectro-
scopic studies of organotin(IV) complexes of biologically active
Schiff bases derived from sulpha drugs. Appl. Organomet. Chem.
2000, 14, 212.
2
2
3. Teoh, S.G. Synthesis crystal structure and biological activity of
thiophene-2-carboxalsehyde thiosemicarbazone and its tin complexes.
J. Organomet. Chem. 1999, 580, 1.
4. Belwal, S.; Singh, R.V. Bioactive versatile azomethine complexes of
organotin(IV) and organosilicon(IV). Appl. Organomet. Chem. 1998, 12,
39.
2
2
2
5. Nicklin, S.; Robson, M.W. Organotins: toxicology and biological
effects. Appl. Organomet. Chem. 1988, 2, 487.
6. Singh, P.P.; Sharma, K.K. Topological aspects of the biological activity
of organotin compounds. Indian J. Chem. 1993, 32B, 551.
7. Casas, J.S.; Garcia-Tasende, M.S.; Sordo, J. Main group metal com-
plexes of semicarbazones and thiosemicarbazones. A structural review.
Coord. Chem. Rev. 2000, 209, 197.

1
908
Singh and Singh
2
2
8. Singh, M.S.; Tripathi, U.N.; Raju, M.D. Synthesis and characterisation
of some organotin(IV) derivatives of 2-(N-salicylidene)-5-chloroben-
zophenone. Main Group Met. Chem. 1997, 20, 497.
9. Singh, M.S.; Raju, M.D.; Tawade, K.; Singh, A.K. Synthesis and
spectroscopic study of some organotin(IV) derivatives of benzilmono-
semicarbazone. Main Group Met. Chem. 1998, 21, 489.
30. Singh, M.S. Synthesis and characterisation of organotin(IV) derivatives
of benzilmonohydrazone. Indian J. Chem. 1998, 37A, 911.
3
1. Singh, M.S.; Raju, M.D.; Singh, A.K.; Narayan, P. Some complexes of
organotin(IV) chloride with salicylaldehyde thiosemicarbazone. Synth.
React. Inorg. Met.-Org. Chem. 1999, 29, 73.
32. Singh, M.S.; Tawade, K.; Singh, A.K. Synthesis and characterisation of
four- and five-coordinate tin(IV) salophenates. Main Group Met. Chem.
1999, 22, 175.
3
3. Singh, M.S.; Raju, M.D.; Singh, P.K.; Tiwari, S.K. Coordination be-
haviour of benzilmonoxime and benzildioxime towards organotin(IV):
synthesis and characterisation. Synth. React. Inorg. Met.-Org. Chem.
1999, 29, 1711.
3
4. Singh, M.S.; Tawade, K. Synthesis and characterisation of some new
organotin(IV) complexes of Schiff bases derived from salicylaldehyde
and hydrazine hydrate. Synth. React. Inorg. Met.-Org. Chem. 2000, 30,
1015.
3
3
3
3
5. Singh, M.S.; Tawade, K. Synthesis and characterization of some
organotin(IV) complexes of benzoin-a-oxime. Synth. React. Inorg.
Met.-Org. Chem. 2001, 31, 157.
6. Singh, M.S.; Singh, B.K.; Tawade, K. Synthesis and characterization of
some new tin(IV) derivatives of NO and N O chelating Schiff bases.
Indian J. Chem. 2001, 40A, 1295.
2
2
7. Singh, M.S.; Tawade, K. Preparation and characterization of some
organotin(IV) complexes of benzilmonoxime thiosemicarbazone as
ligand. Indian J. Chem. 2002, 41B, 419.
8. Singh, M.S.; Singh, A.K.; Tawade, K. N-Benzoin-o-mercaptoaniline as
an efficient synthon for organotin(IV) compounds. Synth. React. Inorg.
Met.-Org. Chem. 2002, 32, 639.
39. Armarego, W.L.F.; Perrin, D.D. Purification of Laboratory Chemicals,
4th Ed.; Butterworth-Heinemann. Oxford OX2 8DP, 1997.
40. Furniss, B.S.; Hannaford, A.J.; Smith, P.W.G.; Tatchell, A.R. Vogel’s
Text Book of Practical Organic Chemistry, 5th Ed.; Longman: UK,
1989.
4
1. Basset, J.; Denney, R.C.; Jeffery, G.H.; Mendham, J. Vogel’s Text Book
of Qualitative Inorganic Analysis, 4th Ed.; Longman: UK, 1978.
2. Sonika; Sharma, S.; Sharma, G.; Narula, A.K. Structural studies on
4

Organotin(IV) Complexes
1909
5- and 6-coordinated unsymmetrical diorganotin(IV) complexes. Indian
J. Chem. 1994, 33A, 1119.
4
3. Wang, J. Synthesis of cyclic rganotin complexes. Prog. Nat. Sci. 1998,
8
, 180.
Received April 29, 2003
Accepted August 12, 2003
Referee I: N. N. Gerasimchuk
Referee II: J. C. Cochran