SYNTHESIS AND INFRARED STUDY OF SOME PHENYLPHOSPHONATE, DIPHENYLPHOSPHINATE AND ACETATOPHOSPHONATE NEW ORGANOTIN (IV) DERIVATIVES AND ADDUCTS

Three organotin (IV) derivatives PhPO3HSnBu2Cl, SnBu2Ph2PO2Cl3/2H2O, Sn(PhPO3)Cl22H2O obtained on allowing PhPO3H2 or propylammonium PhPO3H to react with SnBu2Cl2, SnCl22H2O and two adducts [(C6H5CH2)2NH2]3O2C(CH2)2PO33SnPh3Cl, [CyNH3(HO2POCH2-N(CH2CO2H)2]23SnCl4.2H2ONH4Cl obtained on allowing (C6H5CH2)NH2)3O2C(CH2)2PO3 or [CyNH3(HO2POCH2-N(CH2 CO2H)2]2 and SnPh3Cl or SnCl22H2O to react in ethanolic media have been characterized by elemental analyses, infrared and Mossbauer techniques. The suggested structures, while considering the anionic counterpart, are discrete, dimeric, double and triple metallic components or of infinite chain types, the anion behaving as a monochelating, a bichelating or a bidentate ligand. In OH containing structures, when extra hydrogen bonds are considered, supramolecular architectures may be obtained.


INTRODUCTION
The organotin (IV) compounds are known for several applications in the industrial field (antifouling paints, wood preservatives) and also as drugs against cancer [1,2], that explains the focus of several research teams in the attempt to obtain new molecules of this family [3][4][5]. In the dynamic of our research activity, we have yet published many papers dealing with organotin chemistry [6][7][8][9][10]. In this paper we have initiated the study of the interactions between PhPO3H2, propylammonium PhPO3H, [(C6H5CH2)2NH2]3O2C(CH2)2PO3 or [(CyNH3)(HO2POCH2-N(CH2CO2H)2]2 and SnBu2Cl2, SnCl22H2O or SnPh3Cl which has yielded five new compounds. Infrared and Mossbauer studies were carried out and structures were suggested on the basis of the spectroscopic data.

RESULTS AND DISCUSSION
Let us consider the main infrared data of the studied derivatives and adducts:  The value of the quadrupole splitting of compound A indicates the presence of a trans octahedrally coordinated SnBu2 group according to Parish and Platt [12]: the suggested structure is discrete with a monochelating anion ( Figure 1).
In compound B the value of the quadrupole splitting is consistent with both cis or trans octahedrally coordinated SnCl2 framework.
The suggested structures are reported in Figures 2a, 2b (discrete ones) with the anion behaving as a monochelating ligand or on Figures 2c and 2d (infinite chain structures) with a bidentate anion. The environment around the tin center in all cases is octahedral.
For SnBu2Ph2PO2Cl3/2H2O while considering a dimerization followed by a rearrangement C can be written as: The values of the quadrupole splitting allow to suppose the presence of both a trans octahedrally coordinated SnBu2 residue and a second SnBu2 residue in a trigonal bipyramidal environment according to Parish and Platt [12]. A two metallic components structure may be suggested: -a first metallic component is SnBu2(Ph2PO2 )2 which contains bridging anions and a trans octahedral environment around the tin centre leading to an infinite chain (4.46mms -1 ); -a second metallic component H2OSnBu2Cl2 contains a Sn centre in a bipyramidal trigonal environment (3.16mms -1 ).
These two metallic components may connect via hydrogen bonds to give the structure (Figure 3) (the 2 extra water molecules are considered as lattice).
The discrete suggested structure of compound [D] is reported on Figure 4.  In these structures when the cations are involved in hydrogen bonds a supramolecular architecture may be obtained.

CONCLUSION
The five adducts studied have discrete, dimeric, two or three metallic components or infinite chain type structures, the anion behaving as a monodentate, bidentate, tridentate, mono-or bichelating ligand. The environments of the tin (IV) centres are trigonal bipyramidal or octahedral. In free OH or NH containing structures, when extra hydrogen bonds are considered, supramolecular architectures may be obtained.