Research On Syntheses, Structures And In Vitro Cytotoxic Activity Of Metal Complexes Based On Carborane Ligands Containing Sulfur And Carboxylic Acid

A new field of chemistry was established after the first discovery of polyhedral boraneby Stock early last centery, which brought a new understanding of structural chemistry.After continuous research efforts for nearly a century, the borane chemistry now coversborane, carborane, main group heteroboranes, metallaboranes, metallacarboranes and theirderivatives. Due to their high thermal stability and chemical stability as well as lowtoxicity of carboranes, their application research are fastly developed which involvesmedicine, catalyst, functioanl materials and so on. Based on the previous experimentalresearches of our group on carborane complex contains phosphorus, sulfur and carboxylateacid, two carborane carboxylate acid1-COOH-1,7-C2B10H11,1,7-(COOH)2-1,7-C2B10H10and a thilo-containing carborane ligand1,2-(HS)2-1,2-C2B10H10was selected and theircoordination chemistry was inverstigated in this theme. The four sections of this thesis arelisted below.1. A brief introduction of the development histroy and application of borane chemistryis presented, and the status of current research on metal complex of carborane containingsulfur and carboxylate acid ligand is also reviewed.2. The reactions of1-COOH-1,7-C2B10H11with diorganotin derivatives, indium(Ⅲ)sulfate hydrate, copper(II) acetate and platinum(II) chloride were studied in differentconditions, which afforded six complex:[(Bu2Sn)4O2(OCH3)2(1-OOC-1,7-C2B10H11)2](1),[(Bu2Sn)2(OH)(1-OOC-1,7-C2B10H11)3](2),[Bu2Sn(phen)(1-OOC-1,7-C2B10H11)](3),[In(phen)(1-OOC-1,7-C2B10H11)3](4),{[Cu(phen)2(1-OOC-1,7-C2B10H11)]·(1-OOC-1,7-C2B10H11)}(5) and {[(H2O)2Pt(OH)2Pt(1-OOC-1,7-C2B10H11)]·phen}(6). All complexswere characterized by X-ray single-crystal diffraction and elemental analysis. X-raydiffraction shows that the center Sn atom of complex1-3is penta-coordinated to get atrigonal bipyramidal configuration and complex3are linked by C-H O into1D chainpolymers.. The center In atom of complex4is hexa-coordinated to got an octahedralconfiguration and the molecule of complex4can be linked by C-H O to form1D chainpolymer. The center Cu atom of complex5is penta-coordinated to get a trigonal bipyramidal configuration. The center Pt atom of complex6is tetra-coordinated to got aplanar quadrilateral and a tetrahedron configuration. We studied the cytotoxic activity withthis six complex, and the result shows that complex2has a strong effect on inhibiting thegrowth of HL-60cell line.3. The reactions of1,7-(COOH)2-1,7-C2B10H10(m-CDCH2) with organotin derivatives,indium sulfate hydrate, zinc acetate and potassium acetate were studied at differentconditions which yield seven complex:{[Ph3Sn(m-CDC)]·(2,2-bipy)}n(7),{[Me3Sn(m-CDC)]·(2,2-bipy)}n(8),[(Bu2Sn)2(phen)2(m-CDC)2](9),{[(Bu2SnCl)(m-CDC)]·(NBu4)}2n(10),{[In(phen)2(m-CDCH)2]·(OH)}(11),[Zn4(phen)4(OH)2(m-CDC)3]n(12) and {[(phen)2K(H2O)3(m-CDCH)]·(phen)}(13). These seven complexs were all characterized by X-raysingle-crystal diffraction and elemental analysis. The center Sn atom of complex7,8and10was penta-coordinated to get a trigonal bipyramidal configuration. Complex9ishexa-coordinated to assume an octahedral configuration and the molecule of complex9can be linked into a1D chain polymer by C-H O hydrogen bonds. Complex11ishexa-coordinated to assume an octahedral configuration, and the molecule of complex11can be linked by C-H H-B and C-H O to form1D chain polymer. One center Zn atomof complex12is hexa-coordinated to get an octahedral configuration, and the rest Zn atomis penta-coordinated to assume a trigonal bipyramidal configuration. The center K atom incomplex13is eight coordinated to assume an icosahedron configuration. We studied thecytotoxic activity with this four complex and the test shows that complex7have strongeffects on inhibiting the growth of HL-60cell lines.4. The reactions of1,2-(HS)2-1,2-C2B10H10with diorganotin derivatives andindium(Ⅲ) sulfate hydrate yielded four complex:[Bu2Sn(1,2-S2-1,2-C2B10H10)](14),{[In(2,2-bipy)(1,2-S2-1,2-C2B10H10)2]·[Li(2,2-bipy)2]}(15),{[In(phen)(1,2-S2-1,2-C2B10-H10)2]·[Li(phen)2]·(phen)}(16) and {[In(phen)(1,2-S2-1,2-C2B10H10)2]·[Li(phen)2]·(phen)·(H2O)}(17). These four complex were all characterized by X-ray single-crystal diffractionand elemental analysis. X-ray diffraction test shows that center tin atom of complex14istetra-coordinated to get a tetrahedron configuration. Complex15-17are hexa-coordinatedto get an octahedral configuration, and complex17can be linked by C-H S, O-H N and C-H H-B into1D chain polymer. We studied the cytotoxic activity of this four complexand the result shows that complex14has a moderate effects on inhibiting the growth ofHL-60cell lines.In conclusion, we have synthesized17complex based on there selected three ligands1-COOH-1,7-C2B10H11,1,7-(COOH)2-1,7-C2B10H10,1,2-(HS)2-1,2-C2B10H10, and furtherstudied the in vitro cytotoxic activity of those17complexs. Cytotoxic activity tests showthat some complex have a better effect on inhibiting the growth of the test cells.