Synthesis And Properties Of New Organic Tin Compounds And Complexes

Organotin compounds have been used extensively as insecticides, bactericides, anticancer medicines, and so on. Research in this field has attracted more and more attention. For further investigation in organotin compounds, this thesis provides the synthesize and characterization of a series of organotin compounds and organotin complexes.1. 1,1-Dimethyl-2-ace-tylethyltin trichloride Cl₃SnCMe₂CH₂COMe is synthesized by the reaction of SnCl₂ and (CH₃)₂=CHCOCH₃ in the presence of HC1. It is characterized by means of UV-Vis, IR and 1^H NMR spectra.2. -Methoxycarbonylethyltriphenyltin Ph₃SnCH₂CH₂COOCH₃ is synthesized by the hydrostannation of methyl acrylate with triphenyltin hydride which is the reduction product of Ph₃SnCl by LiAlH₄ A series of β-methoxycarbonylethyldiphenyltin chloride, p-methoxycarbonylethyl-phenyltin dichloride, and p-methoxycarbonylethyltin trichloride, X_nPh_3-nSnCH₂CH₂COOCH₃ (n= 1,2,3; X= Cl , Br or 1) are synthesized by Ph₃SnCH₂CH₂COOCH₃ reacting with halides and characterized by means of elemental analysis, UV-Vis, IR, 1^H NMR spectra.The spectral data show that the ester carbonyl oxygen atom is coordinated to the tin atom, and forms the intramolecular five-memebered structure in compounds 3a -3g. Their structures can be shown as follows:3. The coordination reactions between the compounds X_nPh₍3-n_SnCH₂CH₂COOCH₃ (n=1, 2, 3; X= Cl , Br or 1) and chelating ligands(2,2'-bipyridine, 1,10-phenanthroline, 8-hydroxyquindine, 9-dimethyl -1,10-phenanthroline) are studied, and organotin complexes are prepared and characterized by elemental analysis, UV-Vis, IR and 1^H NMR. The results indicate that in the 1:1 type complexes with DMSO, DMSO does not replace the carbonyl group. But in the 1:2 type complexes with DMSO and the complexes with chelating ligands the carbonyl groups are replaced by the ligands making the C=O groups free. In addition, all the complexes are six-coordinated.4. Complexes of X_nPh_3-nSnCH₂CH₂COOCH₃(n=1, 2, 3)(X=C1, Br or 1) with the Schiff base derived from salicylaldehyde and substituted-aniline are synthesized and characterized by means of elemental analysis, IR and 1^H NMR spectra. The results show that the C=O groups are stillcoordinated with tin atoms, which means that only one donor atoms of the two in the Schiff base ligands is involved in the coordination.5. The single crystal structures of Ph₄Sn, Ph₃SnSnPh₃,I₂PhSnCH₂CH₂ COOCH₃ are determined by X-ray crystallography. The results show that in the crystals of I₂PhSnCH₂CH₂COOCH₃ the tin atom adopts a distorted trigonal bipyramid geometry via intramolecular carbonyl oxygen to tin coordination (the Sn-O bond are 0.243 l(4)nm). The crystals of I₂PhSnCH₂CH₂COOCH₃ are monoclinic with space group P2(l)/n, a=1.1488(5)nm,b=1.1091(5)nm,c=1.1738(5)nm, = 90 , = 104.847(6) , = 90 , V=1.4456(11)nm3, Mr=536.69, Z=4, D=2.466 Mg/m3, =6.020 mm-1, F(000) =976, Reflections collected / unique = 8655 / 3178 [R(int) = 0.0397], Rl = 0.0681, wR2 = 0.0731.and in crystal of Ph3SnSnPh3 are monoclinic with space group P2(1)/n, a = 17.249(10) A, b = 9.369(6)A, c = 20.458(12) A, = 90 ,P = 111.177(8) , = 90 , V=3083(3) A3, Mr=699.08 ,Z=4, D= 1.508 Mg/m3, = 1.642 mm-1, F (000) =1384, Reflections collected / unique= 14472 / 5681 [R(int) = 0.0546], Rl = 0.0998, wR2 = 0.0475.and in crystal of Ph2Sn are tetragonal with space group P-42(l)/n, a = 12.070(4) A, b=12.070(4)A, c = 6.656(12) , = 90 = 90 , = 90 , V = 956.4(6) 3, Mr=427.09, Z=2, D= 1.483 Mg/m3, = 1.338 mm-1, F(000) =428, Reflections collected / unique=5663 /1065 [R(int) = 0.0227], R1 = 0.0271, wR2 = 0.0419...