A New Recipe for diorganotin phosphonate clusters using

dicarboxylatotetraorganodistannoxanes as the precursors

Presented By
Nisha Sharma
2019CYZ8132

Under the guidance of

Prof. Ravi Shankar

Department of Chemistry
Indian Institute of Technology
New Delhi,110016

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 Introduction

 One of the classical topics in organotin chemistry deals with synthesis and structural
aspects of symmetrically and unsymmetrically substituted tetraorganodistannoxanes,
[R2(X)SnOSn(Y)R2]2 (X, Y = carboxylate, halogen, NCS, OH, OSiMe3).

. Novel Sn5O5 hydrolysis structure containing a fourfold ladder featuring a four- membered centrosymmetric Sn 2O2 ring

A. G. Davies, M. Gielan, K. H. Pannell, E. R. T. Tiekink, Tin Chemistry: Fundamentals, Frontiers, and Applications, 2008, p. 201; V. Chandrsekhar, S. Nagendran, V.2 Baskar, Coord. Chem. Rev. 2002, 235, 1–52;
Frenzel, M. Korb, A. Hildebrandt, H. Lang, J. Organomet. Chem. 2018, 870,104–109; C. Ma, J. Zhang, Q. Jiang, R. Zhang, Inorg. Chim. Acta 2004,357, 2791–2797.; D. Daktemieks, K. Jurkschat, D. Schollmeyer, H.
Wu, Organometallics 1994, 13, 4121–4123; D. Dakternieks, A. Duthie, B. Zobel, K. Jurkschat, M. Schürmann, E. R. T. Tiekink, Organometallics 2002, 21, 647–652; J.Beckmann, D. Dakternieks, A. Duthie, F. S.
Kuan, E. R. T. Tiekink, Organo-metallics 2003, 22, 4399–4404; M. Mehring, M. Schürmann, H. ReuteD. Dakternieks, K. Jurkschat, Angew. Chem. Int. Ed. Engl. 1997, 36, 1112–1114; Angew. Chem. 1997, 109,1150.
  Catalytic role of distannoxanes in esterification/transesterification reactions.
 Methods of synthesis include hydrolysis, salt metathesis or azeotropic
dehydration reactions involving diorganotin dichloride or diorganotin oxide as
precursors.
 Extensive NMR studies in solution reveal strong affinity of the dimeric
distannoxanes for structural changes due to labile nature of the metal-ligand
bond enabling ligand exchange and associative dissociative phenomena in
solution.

J. Otera, Acc. Chem. Res. 2004, 37, 288–296 B. Jousseaume,C. Laporte, M.-C. Rascle, T. Toupance, Chem. Commun. 2003, 1428–1429; E. Crawford, T. Lohr, E. M. Leitao, S. Kwok,
J. S. McIndoe, Dalton Trans. 2009, 9110–9112; G.-L. Zheng, J.-F. Ma, J. Yang, Y.-Y. Li, X.-R. Hao, Chem. Eur. J. 2004, 10,3761–3768; A. S. Sougoule, Z. Mei,
3 X. Xiao, C. A. Balde,
S. Samoura, A. Dolo, D. Zhu, J. Organomet. Chem. 2014, 758, 19–24; X. Xiao, K. Shao, L. Yan, Z. Mei, D. Zhu, L. Xu, Dalton Trans. 2013, 42, 15387–15390; R.-H. Wang, M.-C.
Hong, J.-H. Luo, R. Cao, J.-B. Weng, Eur. J. Inorg. Chem.2002, 2082–2085; b) R.-F. Zhang, Q.-F. Wang, M.-Q. Yang, Y.-R. Wang, C.- L. Ma, Polyhedron 2008, 27, 3123–3131.
.
 Proposed monomer-dimer equilibrium and 119Sn NMR spectrum of an equimolar mixture
of ClBu2SnOSnBu2(OMe) plus [Bu2SnCl]2O in C6D6 results in the eight-line spectrum
shown as:

 Reversible ligand-exchange reaction occurs where [Bu 2SnCl]2O is combined with

[Bu2Sn(O2CMe)]2O

D. C. Gross, Inorg. Chem. 1989, 28, 2355–2359;

 Prior Work : Synthesis of triorganotin-based coordination assemblies
derived from ambidentate phosphonate and sulfonate ligands

3n Et2Sn(OMe)(OSO 2 Me) 2n MeP(O)(OH)2

CHCl3
rt, 8h

[(Et2Sn)3 (O 3PMe)2 (OSO 2Me)2.CHCl3 ]n 3n MeOH n MeSO 3 H

Proposed mechanism:

Shankar, R.S.; Jain, A.; Kociok-Kohn, G.; Molloy, K.C.; Inorg. Chem. Acta, 2011, 372, 108-114.
 Work Done

 Distannoxanes, 1-3 have been synthesized by azeotropic dehydration reaction of n-

dibutyltin oxide and ortho-substituted benzoic acids in toluene.

Toluene
4 n-Bu 2SnO + 4 RCOOH [{Bu 2Sn(O 2CR)}2O]2 2 H 2O
reflux, 4 - 5 h
R = o-C 6H 4Cl(1), o-C 6H 4OH(2), o-C 6H 4Br(3)

Narula, S.P.; Bhardwaj, S.K.; Sharda, Y.; Organometallics, 1992, 11, 2206-2211; Abdellah, M.A.; Hadjikakou, S.K.; Hadjiliadis, N.; Maciej K.;6 Bakas, K.;
Kourkoumelis, N.; Simos, Y.V.; Karkabounas, S.; Barsan, M.M.; Butler, I.S.; Bioinorg Chem Appl, 2009, 12, 542979; Matela. G; Aman R.; Cent. Eur. J. Chem, 2012,
10, 1-15.
 Characterisation

IR (cm-1): 560 (ν Sn-C),

630 (ν Sn-O-Sn)

1
H NMR spectrum of [{Bu2Sn(o-O2CC6H4Cl}2O]2
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 Synthesis of [(Bu2Sn)3(OPO3But)3(RCOOH)]

 Reactions of 1 and 2 with two equivalents of t-butylphosphonic acid in

dichloromethane – methanol mixture (1:4) proceed under ambient conditions as shown
below :

3n[{Bu 2Sn(O 2CR)}2O]2 + 6n t -BuP(O)(OH)2

DCM : MeOH (1 :4)

stir, 24h

2n [(Bu 2Sn)3(O 3PBu t)(HO 2CR)] 10n RCOOH

R = o-C 6H 4Cl(4), o-C 6H 4OH(5)

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 Characterisation

31
P NMR spectrum

1
H NMR and IR spectrum of 5

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Crystal Structure of 4 and 5

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THANK YOU

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