Synthesis and characterization of some organotin(IV) complexes of α-benzoin oxime

Article abstract of DOI:10.1081/SIM-100001941

Some di-and triorganotin(IV) complexes of α-benzoin oxime of the general formulae R₃SnL, R₂SnCl_2-nL_n, and R₂SnL have been synthesized by the reactions of the corresponding di-and triorganotin(IV) chlo

Full text of DOI:10.1081/SIM-100001941

This article was downloaded by: [Tulane University]
On: 29 September 2014, At: 10:55
Publisher: Taylor & Francis
Informa Ltd Registered in England and Wales Registered Number: 1072954 Registered office: Mortimer
House, 37-41 Mortimer Street, London W1T 3JH, UK
Synthesis and Reactivity in Inorganic and Metal-
Organic Chemistry
Publication details, including instructions for authors and subscription information:
http://www.tandfonline.com/loi/lsrt19
SYNTHESIS AND CHARACTERIZATION OF SOME
ORGANOTIN(IV) COMPLEXES OF α-BENZOIN OXIME
M. S. Singh a & K. Tawade a
a Department of Chemistry , Deen Dayal Upadhyaya Gorakhpur University , Gorakhpur,
U.P., 273 009, India
Published online: 20 Aug 2006.
To cite this article: M. S. Singh & K. Tawade (2001) SYNTHESIS AND CHARACTERIZATION OF SOME ORGANOTIN(IV)
COMPLEXES OF α-BENZOIN OXIME, Synthesis and Reactivity in Inorganic and Metal-Organic Chemistry, 31:1, 157-165, DOI:
10.1081/SIM-100001941
To link to this article: http://dx.doi.org/10.1081/SIM-100001941
PLEASE SCROLL DOWN FOR ARTICLE
Taylor & Francis makes every effort to ensure the accuracy of all the information (the “Content”) contained
in the publications on our platform. However, Taylor & Francis, our agents, and our licensors make no
representations or warranties whatsoever as to the accuracy, completeness, or suitability for any purpose of
the Content. Any opinions and views expressed in this publication are the opinions and views of the authors,
and are not the views of or endorsed by Taylor & Francis. The accuracy of the Content should not be relied
upon and should be independently verified with primary sources of information. Taylor and Francis shall
not be liable for any losses, actions, claims, proceedings, demands, costs, expenses, damages, and other
liabilities whatsoever or howsoever caused arising directly or indirectly in connection with, in relation to or
arising out of the use of the Content.
This article may be used for research, teaching, and private study purposes. Any substantial or systematic
reproduction, redistribution, reselling, loan, sub-licensing, systematic supply, or distribution in any
form to anyone is expressly forbidden. Terms & Conditions of access and use can be found at http://
www.tandfonline.com/page/terms-and-conditions

SYNTH. REACT. INORG. MET.-ORG. CHEM., 31(1), 157–165 (2001)
SYNTHESIS AND CHARACTERIZATION OF
SOME ORGANOTIN(IV) COMPLEXES OF
α-BENZOIN OXIME
M. S. Singh∗ and K. Tawade
Department of Chemistry, Deen Dayal Upadhyaya
Gorakhpur University, Gorakhpur 273 009 (U.P.), India
ABSTRACT
Some di- and triorganotin(IV) complexes of α-benzoin oxime
of the general formulae R3SnL, R2SnCl2−nLn, and R2SnL have
been synthesized by the reactions of the corresponding di- and tri-
organotin(IV) chlorides with the sodium salt of α-benzoin oxime
in the desired molar ratios. All of the compounds have been charac-
terized by elemental analyses and spectral (IR, 1H, 13C, and 119Sn
NMR) studies.
INTRODUCTION
Complexes of organotin(IV) halides with N, O, and S donor ligands have
received much attention during the last few years (1–4). The considerable devel-
opments over recent decades in the use of organotin compounds as reagents (5)
or intermediates in organic synthesis (6,7) prompted the preparation of many new
organotin compounds. Certain penta- and hexa-coordinated organotin(IV) com-
plexes (8), a number of oximates (9), and complexes of titanium with α-benzoin
∗Corresponding author. E-mail: dr m s singh@yahoo.com
157
Copyright ꢀ 2001 by Marcel Dekker, Inc.
www.dekker.com
C

ORDER
REPRINTS
158
SINGH AND TAWADE
oxime (10) have been reported in the literature. A recent review deals with com-
plexes of oximes and oximato species (11). Organotin compounds having the
general formula RnSnCl4−n are biologically active (12–16) and have been used in
carbohydrate and nucleoside chemistry (17). Thus, in view of the synthetic and bi-
ological importance of organotin(IV) compounds and in continuation of our recent
report on organotin(IV) (18–21), we report here the synthesis and characterization
of some new organotin(IV) complexes of α-benzoin oxime.
RESULTS AND DISCUSSION
α-Benzoin oxime was synthesized by the condensation of benzoin and
hydroxylamine hydrochloride in 1:1 molar ratio (22,23). Triorganotin(IV) and
diorganotin(IV) derivatives of α-benzoin oxime with the general formulae R3SnL,
R2SnLnCl2−n, and R2SnL have been synthesized by the reaction of the correspond-
ing triorganotin(IV) and diorganotin(IV) chlorides with the conjugate base of the
ligand H2L (prepared in situ) by using sodium hydride in 1:1 and 1:2 molar ratios,
respectively.
H
OH
N
O
+
R3SnCl
benzene
−
O Na+
SnR3
(1)
i-PrOH
-NaCl
N
O
R = Ph, (1); R = n-Bu, (2).
H
O
OH
+
R2SnCl2
n
benzene
−
O Na+
SnR2Cl2−n
(2)
i-PrOH
-n NaCl
N
N O
n
n = 1, R = Me, (3); n = 1, R = n-Bu, (4), n = 2, R = Me, (5), n = 2, R = n-Bu, (6).
Similarly, diorganotin(IV) complexes of the type R2SnL have been synthe-
sized from the dianion of the ligand.
All of these new complexes were characterized on the basis of satisfactory
elemental analyses and spectral data. These compounds are more or less soluble

ORDER
REPRINTS
ꢀ-BENZOIN OXIME COMPLEXES
159
R
−
+
O
N
O Na
Sn
O
(3)
+
R2SnCl2
n
benzene
R
−
+
O Na
i-PrOH
-2 NaCl
N
R = Me, (7); R = n-Bu, (8).
in common organic and coordinating solvents like C6H6, CHCl3, CH2Cl2, CCl4,
DMF, and DMSO. Molecular weight determinations in dilute CHCl3 show the
monomeric nature of these complexes.
Infrared Spectra
The IR spectral data of the complexes have been recorded in Nujol in the
range of 4000–200 cm−1. The IR spectrum of the ligand (H2L) shows bands in the
regions 3360–3240, 3482, and 1590 cm−1 assignable to ν(OH) of the CH−OH
group, ν(OH) of the =N−OH group and ν(C=N), respectively. The disappearance
of absorption bands and signals corresponding to ν(OH) of the >CH−OH and
=N−OH groups in the IR spectra of the complexes (7) and (8) suggest a cyclic
structure. Thisfactisfurthersupportedbytheappearanceofnewbandsintheregion
580–440 cm−1, which are ascribed to Sn−C and Sn−O stretching modes (24–26).
A strong band at 1590 cm−1 assignable to ν(C=N) in the free ligand remains as
such in the spectra of all the complexes, clearly indicating the noninvolvement
of C=N in complexation (24). In compounds (1)–(6) that have been synthesized
from the monoanion, the >CHOH group takes part in complexation, which is
further supported by the shift of the ν(OH) frequency to lower wave number
(ca. 3130 cm−1 ) in the spectra of the complexes.
Nuclear Magnetic Resonance Spectra
1
The H, 13C, and 119Sn spectra of the complexes have been recorded in
CDCl3 and DMSO-d6 using TMS as an internal standard and tetramethyltin as
external standard respectively, and the observed chemical shifts are tabulated in
1
Table 1. The H NMR spectra of the complexes exhibit the usual features. A
1
comparison of the H NMR spectral data of the free ligand with the complexes
exhibits the disappearance of the signal at δ10.6 ppm in compounds (1)–(6),

ORDER
REPRINTS
160
SINGH AND TAWADE

ORDER
REPRINTS
ꢀ-BENZOIN OXIME COMPLEXES
161
suggesting the deprotonation of =N−OH and complexation with tin metal (25,26).
The >CH−OH group in the ligand appears at δ 5.61 ppm, shifts downfield (to δ
6.20 ppm) in the complexes, indicating its deshielding and coordination through
the oxygen of the >CH−OH group to tin metal in compounds (1)–(6). The res-
onance due to the phenyl moiety at δ 7.32–7.15 ppm remains almost unaffected
in all the complexes. The resonances due to butyl tin protons are observed in the
region δ 0.70–1.16 ppm (J = 8 Hz), which is due to terminal methyl protons of
butyl group. The methyl protons of dimethyl tin(IV) derivatives appear as a sharp
singlet at δ 0.88 ppm. The coupling constants provide valuable information about
1
the hybridization state of tin (21,24). The 2J(119Sn− H) values in the range 54–68
Hz are indicative of four-coordinate tin in compounds (7) and (8). The tin–proton
1
coupling constants, 2J(119Sn− H) in compounds (1)–(6) have been found at 87
1
Hz, which is indicative of a higher coordination number (five and six) of tin (24),
suggesting the bidentate behaviour of the ligand.
The 13C NMR spectra of the complexes show the expected number of signals.
The δ 10–15 ppm downfield signal shifts of carbons attached to oxygen indicate
oxygen coordination with the tin atom. The R groups attached to tin display a single
resonance for chemically equivalent carbons. The 1J(119Sn− C) values occur in
13
the range for four-(7), five- and six-coordinated tin (27,28).
The 119Sn NMR chemical shifts of these complexes have been observed
in the range δ 132.8 to –352.6 ppm and suggest that these compounds contain
four-(7), five- and six-coordinated tin (28).
EXPERIMENTAL
All reactions were carried out under a nitrogen atmosphere and analytical
grade chemicals were used. Solvents used were purified and dried according to
standard procedures (29). The progress of the reaction and purity was checked by
TLC on silica gel. The ligand was synthesized by the literature method (22,23). Ele-
mental anslyses were performed by the Central Drug Research Institute, Lucknow.
Tin and chloride in the complexes were determined gravimetrically or messenger’s
method, respectively (30).
IR spectra were recorded on a Perkin–Elmer model 377 spectrometer in
the range 4000–200 cm−1. NMR spectra were recorded on a Bruker AC200 in-
1
strument at 200, 74, and 50.32 MHz for H, 119Sn, and 13C, respectively at the
National Chemical Laboratory, Pune. Chemical shifts are in ppm and relative
1
to TMS for H and 13C, and tetramethyltin for 119Sn as an internal standard,
respectively.
α-Benzoin oxime: m.p. 151◦C
1H NMR (CDCl3): δ 10.6 (s, 1H, N−OH); 7.32–7.15 (m, 10H, Ph); 5.61
(s, 1H, OH); 2.95 (s, 1H, CH).

ORDER
REPRINTS

ORDER
REPRINTS
ꢀ-BENZOIN OXIME COMPLEXES
163
IR (Nujol, cm−1): ν(C=N) 1590, ν(OH) 3360–3240, ν(N−OH) 3482.
Analysis found: C, 73.84; H, 5.54; N, 5.96. Calcd. for C14 H13 NO2 (227):
C, 74.01%; H, 5.73%; N, 6.17%.
Reaction Between Triphenyltin(IV) Chloride and the Sodium Salt
of ꢀ-Benzoin Oxime in 1:1 Molar Ratio
A quantity of 0.050 g (2.08 mmol) of sodium hydride and 15 mL of iso-
propanol were placed in a two neck round bottom flask fitted with a dried and
cooled water condenser and a dropping funnel. The mixture was stirred for about
30 min till a clear solution of sodium isopropoxide was obtained. Then 0.474 g
(2.08 mmol) of α-benzoin oxime was added to the sodium isopropoxide solution.
The mixture was refluxed for 2 h. The light yellow solution changed to brown
after 2 h. Then a solution of 0.803 g (2.08 mmol) of triphenyltin(IV) chloride in
benzene was added slowly by a dropping funnel at room temperature. The colour
of the mixture changed to milky white. It was further refluxed for 2–3 h to ensure
the completion of the reaction, checked by TLC. The desired product was isolated
by filtering off the precipitated sodium chloride and evaporation of the solvent
under reduced pressure. The product was further purified by crystallization from
benzene–petroleum ether (40–60◦C) mixture (20 mL each).
All other organotin(IV) derivatives of α-benzoin oxime were synthesized
analogously. The pertinent data for this and other derivatives are listed in Table 2.
ACKNOWLEDGMENT
The authors are highly grateful to the Council of Scientific & Industrial
Research, New Delhi, India.
REFERENCES
1. Mehrotra, R.C.; Srivastava, G.; Saraswat, B.S. Rev. Silicon, Germanium, Tin
and Lead Compounds 1982, 6, 171.
2. Nath, M.; Yadav, R. Bull. Chem. Soc. Jpn. 1997, 70, 1331; Kumari, A.; Singh,
R.V.; Tandon, J.P. Indian J. Chem. 1991, 30A, 468; Visalakshi, R.; Jain, V.K.;
Kulshreshtha, S.K.; Rao, G.S. Indian J. Chem. 1989, 28A, 51.
3. Rao, R.J.; Wankhade, H.B. Synth. React. Inorg. Met.-Org. Chem. 1995, 25,
1049; Rao, R.J.; Wankhade, H.B. Main Group Met. Chem. 1996, 19, 4;
Saraswat, B.S.; Mason, J. Polyhedron 1986, 5, 1449.
4. Singh, M.S.; Tripathi, U.N.; Raju, M.D. Main Group Met. Chem. 1997, 20,
497; Singh, M.S.; Raju, M.D.; Tawade, K.; Singh, A.K. Main Group Met.
Chem. 1998, 21, 489.

ORDER
REPRINTS
164
SINGH AND TAWADE
5. Mitchell, T.N. Met Catal Cross Coupling Reaction; Diedrich, F., Stang, P.J.,
Eds.; Wiley VCH: Weinheim, Germany, 1998; 167.
6. Davies, A.G.; Smith, P.J. Comprehensive Organometallic Chemistry;
Wilkinson, G. Stone, F.G.A. Abel, E.W. Pergamon: Oxford, U.K., 1982;
Pereyre, M.; Quintard, J.P.; Rahm, A. Tin in Organic Synthesis; Butterworth:
London, 1987, 185; Yamamoto, Y. Acc. Chem. Res. 1987, 20, 243.
7. Morton, D.; Russo, U.; Stivanello, D.; Tagliavini, G. Organometallics 1996,
15, 1645.
8. Bhambhani, S.; Saxena, S.; Rai, A.K. Main Group Met. Chem. 1995, 18,
251.
9. Sevindir, H.C. Synth. React. Inorg. Met.-Org. Chem. 1996, 26, 1351; Singh,
A.; Gupta, V.D.; Shrivastava, G.; Mehrotra, R.C. J. Organomet. Chem. 1974,
64, 145.
10. Singh, M.S.; Narayan, Prem. Indian J. Chem., in press.
11. Wong, C.Y.; Woollins, J.D. Coord. Chem. Rev. 1994, 130, 175.
12. Barnes, J.M.; Magos, L. Organomet. Chem. Rev. 1968, 3, 137.
13. Smith, P.J. Toxicological Data on Organotin Compounds; International Tin
Research Institute: London, 1978; Elliot, B.M.; Aldridge, W.N.; Brides, J.W.
Biochem. J. 1979, 177, 461.
14. Sonika, S.; Sharma, S.; Gupta, S.; Narula, A.K. Indian J. Chem. 1994, 33A,
1119.
15. Cardin, C.J.; Roy, A. Inorg. Chim. Acta 1985, 107, 57.
16. Nicklin, S.; Robson, M.W. Appl. Organomet. Chem. 1988, 2, 487.
17. Blunden, S.J.; Cusack, P.A.; Smith, P.J. J. Organomet. Chem. 1987, 325, 141.
18. Singh, M.S. Indian J. Chem. 1998, 37A, 911.
19. Singh, M.S.; Tawade, K.; Singh, A.K. Main Group Met. Chem. 1999, 22,
175.
20. Singh, M.S.; Raju, M.D.; Singh, A.K.; Narayan, P. Synth. React. Inorg. Met.-
Org. Chem. 1999, 29, 73.
21. Singh, M.S.; Raju, M.D.; Singh, P.K.; Tiwari, S.K. Synth. React. Inorg. Met.-
Org. Chem. 1999, 29, 1711.
22. Furniss, B.S.; Hannaford, A.J.; Smith, P.W.G.; Tatchell, A.R. Vogel’s Text
Book of Practical Organic Chemistry, 5th Edn.; Longman, U.K, 1989.
23. Dreos, R.; Tauzher, G.; Trendafilova, D.H.; Nardin, G.; Randaccio, L.
Inorg. Chem. 1996, 35, 2715; Kerr, K.A.; Robertson, J.M.; Sim, G.A.
Chem. Commun. 1967, 170.
24. Srivastava, T.N.; Chauhan, A.K.S.; Agarwal, M. J. Inorg. Nucl. Chem. 1979,
41, 896.
25. Sharma, R.K.; Singh, R.V.; Tandon, J.P. J. Inorg. Nucl. Chem. 1981, 43, 410.
26. Gupta, A.K.; Sharma, S.; Chouhan, H.P.S.; Rao, R.J. Synth. React. Inorg.
Met.-Org. Chem. 1991, 21, 497.
27. Nath, M.; Goyal, S. Main Group Met. Chem. 1993, 16, 167.

ORDER
REPRINTS
ꢀ-BENZOIN OXIME COMPLEXES
165
28. Jain, V.K.; Mason, J.; Saraswat, B.S.; Mehrotra, R.C. Polyhedron. 1985, 4,
2089; Saxena, A.; Tandon, J.P. Polyhedron. 1984, 3, 681.
29. Armarego, W.L.F.; Perrin, D.D. Purification of Laboratory Chemicals, 4th
Edn.; Butterworth: Oxford, 1997.
30. Basset, J.; Denney, R.C.; Jeffery, G.H.; Mendham, J. Vogel’s Text Book of
Qualitative Inorganic Analysis, 4th Edn.; Longman: U.K., 1978.
Received July 8, 2000
Referee I: L. K. Krannich
Accepted November 9, 2000
Referee II: E. Mascowski, Jr.

Request Permission or Order Reprints Instantly!
Interested in copying and sharing this article? In most cases, U.S. Copyright
Law requires that you get permission from the article’s rightsholder before
using copyrighted content.
All information and materials found in this article, including but not limited
to text, trademarks, patents, logos, graphics and images (the "Materials"), are
the copyrighted works and other forms of intellectual property of Marcel
Dekker, Inc., or its licensors. All rights not expressly granted are reserved.
Get permission to lawfully reproduce and distribute the Materials or order
reprints quickly and painlessly. Simply click on the "Request
Permission/Reprints Here" link below and follow the instructions. Visit the
U.S. Copyright Office for information on Fair Use limitations of U.S.
copyright law. Please refer to The Association of American Publishers’
(AAP) website for guidelines on Fair Use in the Classroom.
The Materials are for your personal use only and cannot be reformatted,
reposted, resold or distributed by electronic means or otherwise without
permission from Marcel Dekker, Inc. Marcel Dekker, Inc. grants you the
limited right to display the Materials only on your personal computer or
personal wireless device, and to copy and download single copies of such
Materials provided that any copyright, trademark or other notice appearing
on such Materials is also retained by, displayed, copied or downloaded as
part of the Materials and is not removed or obscured, and provided you do
not edit, modify, alter or enhance the Materials. Please refer to our Website
User Agreement for more details.
Order now!
Reprints of this article can also be ordered at
http://www.dekker.com/servlet/product/DOI/101081SIM100001941