| The coordination chemistry of antimony has both a practical and theoretical interest. The medicinal and cosmetic use of antimony complexes goes back at least to the Egyptians. Potassium antimony tartrate or tartar emetic was widely used until the early 1900s despite the somewhat toxic nature of the material. On the other hand, antimony complexes have been reported with good cytotoxicity and antitumor activities. After many year research and development, antimony complexes has been widely used in polymer compound and medicinal.Sb(III) exhibits a highly variable coordination number and often an irregular coordination geometry. In addition, due to the versatile coordination and connecting mode of dithiocarbamate and xanthate, to date, a large number of transition-metal complexes with dithiocarbamate and xanthate have been synthesized and structurally characterized, including Ni(S2CNC4H8O)2,Cu(S2CNC4H8)2,Zn(S2CNC4H8O)2,Fe(S2CNC4H8O)2(DMF) Cd(S2CO-n-C4H9)2,Cu(C6H11OCS2)2(phen).However, the chemistry of main-group metal complexes with dithiocarbamate has been scarcely studied, and a few reports have appeared on the synthesis and structures of the antimony(III) complexes with dithiocarbamate. Through its versatile coordination and connecting mode of dithiocarbamate and xanthate, we have synthesized some antimony (III) complexes with dithiocarbamate and xanthate, and determined its structure by using X-ray single-crystal diffraction. Furthermore, their spectral properties and molecular structures have been studied carefully with elemental, IR analyses, NMR (1H, 13C) spectroscopy and single crystal X-ray diffraction. According to the difference of their structures, the main contributions of the thesis are as follows: 1. Preparations of a series of N, N-dialkyldithiocarbamate R2NCS2Na (R2N= Me2N, Et2N, (CH2)4N, (CH2)5N, O(CH2CH2)2N, C6H12N, Cy2N, Bz2N, MeN(CH2CH2)2N, EtN(CH2CH2)2N, BzN(CH2CH2)2N, (HOCH2CH2)2N) and O-alkylxanthate ROCS2Na(RO= MeO, EtO, ?-PrO, n-BuO, ?-BuO, C6H11O, C6H5CH2O).2. Synthesize a series of chloridoantimony(III) compounds by reaction of antimony chloride with N,N-dialkyldithiocarbamate in different stoichiometry. Their spectral properties and molecular structures have been studied carefully with elemental, IR analyses, NMR (1H, 13C) spectroscopy and single crystal X-ray diffraction. The results show that complexes 3.1, 3.8 are associated into dimers through intermolecular weak Sb…S interactions, but there is not Sb…S interactions in complex 3.10. Interestingly, all these complexes are further linked to 2D network or 3D framework supramolecular structures through intermolecular C-H…Cl,C-H…O,C-H…S weak hydrogen bonds.3. Synthesize a series of bromicantimony(III) compounds by reaction of antimony bromide with N,N-dialkyldithiocarbamate in different stoichiometry. Their spectral properties and molecular structures have been studied carefully with elemental, IR analyses, NMR (1H, 13C) spectroscopy and single crystal X-ray diffraction. The results show that complexes 4.1-4.3 are linked by weak Sb…S interactions into dimmer or 1D chain,. And these molecules are further linked to form 2D network or 3D framework supramolecular structures through intermolecular C-H…Br and O-H…O interactions.4. Synthesize a series of iodoantimony(III) compounds by reaction of antimony iodide with N,N-dialkyldithiocarbamate in different stoichiometry. Their spectral properties and molecular structures have been studied carefully with elemental, IR analyses, NMR (1H, 13C) spectroscopy and single crystal X-ray diffraction. The results show that in the iodoantimony(III) derivatives the products are linked by iodide atoms forming dimmer or 1D chain. In complex 5.1 and 5.4 these molecules are further linked to form 2D network or 3D framework supramolecular structures through intermolecular C-H…I and C-H…S interactions.5. Synthesize a series of new halogenated antimony(III) compounds by reaction of antimony halogen with xanthate in different stoichiometry. Their spectral properties and molecular structures have been studied carefully with elemental, IR analyses and NMR (1H, 13C) spectroscopy. The results show that the central antimony atoms are coordinated by xanthate in bidentate fashion.6. Synthesize eight new halogenated antimony(III) compounds by reaction of antimony halogen with N-donor neutral ligands (1, 10-phenanthroline, 4,4′-bipyridine) in different stoichiometry. Their spectral properties and molecular structures have been studied carefully with elemental, IR analyses, NMR (1H, 13C) spectroscopy and single crystal X-ray diffraction. The result show that these complexes are linked byπ…πstacking interactions or C-H…Br, N-H…Br, N-H…O weak hydrogen bonds, forming 1D chain,2D network or 3D framework supramolecular structures.
|
PDF Full Text Request