Study On Syntheses,Characterization And Supramolecular Structures Of Bismuth(Ⅲ) Complexes With Ligands Of N,N-dialkyldithiocarbamate And Xanthate

Due to the nontoxic characters of bismuth and pebiological activities, bismuth(III) complexes have been extensively investigated. Bismuth compounds are used for the treatment of gastrointestinal disorders and may also be useful for the treatment of other diseases. Bi(III) exhibits a highly variable coordination number (3-10) and often an irregular coordination geometry. To date, a large number of transition-metal complexes with dithiocarbamate have been synthesized and structurally characterized, including Ni(S₂CNC₄H₈O)₂,Cu(S₂CNC₄H₈)₂,Zn(S₂CNC₄H₈O)₂,Fe(S₂CNC₄H₈O)₂(DMF).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 bismuth(â…¢) complexes with dithiocarbamate. Through its versatile coordination and connecting mode of dithiocarbamate and xanthate, we have synthesized some bismuth (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 studies carefully with elemental, IR and single crystal X-ray diffraction. According to the difference of their structures, the main contributions of the thesis are as follows:1,Preparations 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) and O-alkylxanthate ROCS₂Na(RO= EtO, i-PrO, i-BuO)。2,Syntheses eight new nitrate bismuth(III) compounds by reaction of bismuth nitrate with N,N-dialkyldithiocarbamate or 1,10-Phen or 2,2'-Bpy in different stoichiometry. Their spectral properties and molecular structures have been studies carefully with elemental, IR analyses and single crystal X-ray diffraction. The results show that geometry configuration of these bismuth(III) compounds are usually depicted as monomeric. The dithiocarbamate ligands all are linked to central tin atoms in an bidentate fashion. According to the Bi-S distances and reaction condition, we find that the greater spatial resistence from alkyl group is, the weaker the bismuth-sulfur coordination bond is, the harder reaction condition is. The sequence is N,N-dibenzyl> N -benzylpiperazinyl>piperidyl. Interestingly, these molecules are further linked to 1D or 2D supramolecular structures through intermolecular C-H···S and C-H···O interactions.3,Syntheses five new chlorobismuth(III) compounds by reaction of bismuth chloride with N,N-dialkyldithiocarbamate or 1,10-Phen in different stoichiometry. Their spectral properties and molecular structures have been studies carefully with elemental, IR analyses and single crystal X-ray diffraction. The results show that in the chlorobismuth derivatives of N -benzylpiperazinyldithiocarbamate, the products are thirty-four-nuclear macrocycles and their structures don't display apparent difference. Interestingly, these macrocyclic molecules are further linked to 1D or 2D supramolecular structures through intermolecular C-H···S interactions.4,Syntheses four new bromicbismuth(III) compounds by reaction of bismuth bromide with N,N-dialkyldithiocarbamate in different stoichiometry. Their spectral properties and molecular structures have been studies carefully with elemental, IR analyses and single crystal X-ray diffraction. The results show that in the bromicbismuth(III) derivatives of N,N-dialkyldithiocarbamate, the products are dimmer,six-nuclear macrocycles,1D. And these molecules are further linked to form 1D or 2D supramolecular structures through intermolecular C-H···Br and C-H···S interactions.5,Syntheses nine new iodobismuth(III) compounds by reaction of bismuth iodide with N,N-dialkyldithiocarbamate or 1,10-Phen or 4,4'-Bpy in different stoichiometry. Their spectral properties and molecular structures have been studies carefully with elemental, IR analyses and single crystal X-ray diffraction. The results show that in the iodobismuth(III) derivatives the products linked by iodide atoms are dimmer,1D. And these molecules are further linked to form 1D or 2D supramolecular structures through intermolecular C-H···I and C-H···S interactions.6,Syntheses nine new halogenated bismuth(III) compounds by reaction of bismuth halogen with xanthate or 1,10-Phen in different stoichiometry. Their spectral properties and molecular structures have been studies carefully with elemental, IR analyses and single crystal X-ray diffraction. The results show that in the bismuth halogen with xanthate and 1,10-Phen, the products are further linked to 1D network through intermolecularπ···πand C-H···S interactions. Reaction of bismuth halogen with ?-BuOxanthate under solvothermal condition and obtained a coordination polymer, [Bi(S₂COC3H7)3]n. In this coordination polymer, the products are further linked to 1D network through intermolecular Bi···S interactions.