| More than one century has past when Werner established the coordinate theory in 1893.During this period of time, the coordination chemistry has been developed vigorously as a branch of inorganic chemistry. Salamo-type compounds, which are prepared by the condensation of aldehydes, ketones or their derivatives with amines, are ligands of great importance because of their excellent coordinating ability to transition metal ions.Salamo-type transition metal complexes formed by coordinating Salamo-type compounds with transition metal ions possess some special properties such as REDOX ability, catalytic ability and ability of being used as functional materials in some cases. Many of the complexes have also shown good antiphthisic, anticancer and antibacterial activities.Salamo-type transition metal complexes have already demonstrated their potential applications in many areas such as catalysis. Therefore, it will contribute a lot of the development of coordination chemistry to prepare new complexes with Salamo-type ligands and study their structure-activity relationship or develop their potential applications.In this thesis, a new kind of diamines(1,2-bis(aminooxy)ethane) was synthesized. Then it reacted with 2,4-dihydroxyacetophenone respectively. After purification by column chromatography, single condensation product of ethylene oxide single condensing1,2-diamine 2,4-dihydroxyacetophenone was obtained,respectively. Reactions of ethylene oxide single condensing 1,2-diamine 2,4-dihydroxyacetophenone with2,3-dihydroxybenzaldehyde and 3,5-dichlorosalicylaldehyde provided two asymmetric Salamo compounds H4L1 and H3L2, respectively. Reaction of diamines and2,4-dihydroxyacetophenone also provided structurally symmetric product of double condensation H4L3. The last diamines reacted with 3,5-dibromosalicylaldehy respectively,and purification by column chromatography, single condensation product of ethylene oxide single condensing 1,2-diamine 3,5-dibromosalicylaldehy was obtained,respectively.Reactions of ethylene oxide single condensing 1,2-diamine 3,5-dibromosalicylaldehy with5-Chlorosalicylaldehy provided one asymmetric Salamo compounds H2L4, respectively.The structures of these ligands have been characterized by elemental analyses, IR spectra,1H-NMR, etc.A series of new double oxime Ni(II), Co(II) complexes were synthesized by these ligands with Ni(II), Co(II) reaction in an organic solvent. In different solvent systems, by solvent evaporation method natural, liquid diffusion method and hydrothermal method, cultivate a ligand and three novel Co(II), Ni(II) complexes single crystal material:1. H4L3; 2. [Ni(L4)(C5H5N)]2; 3. [{Co3(HL1)(Me O)(Me OH)(Et OH)(OAc)2}2]·2Et OH; 4.[{Co3(HL1)(Me O)(Me OH)2(OAc)2}2]·2Me OH.The structures of these ligands and complexes have been determined by X-ray single crystal diffraction, and the preliminary conclusion of the coordination modes of such complexes has been deduced. The main crystal data are listed as following:H4L3: empirical formula: C18H20N2O6·H2O, Mr: 378.38, Triclinic, space group: P-1, cell parameters: a = 6.874(4) ?, b = 9.627(6) ?, c = 13.925(9) ?, α = 76.879(9)°, β =85.376(10)°, γ = 86.023(9)°, Z = 2, V = 893.3(10) ?3, R1 = 0.1170(1807), w R2 =0.1678(3993);Complex 1: empirical formula: C42H32Br4Cl2Ni2N6O8, Mr: 1256.62, Orthorhombic, space group: Pbca, cell parameters: a = 14.5792(3) ?, b = 16.9377(4) ?, c = 18.0277(4) ?, α = 90°,β = 90°, γ =90°, Z = 4, V = 4451.73(17) ?3, R1 = 0.0482(3776), w R2 = 0.1331(4201);Complex 2: empirical formula: C50H68Co6N4O26·2Et OH, Mr: 1586.80, Monoclinic, space group: C 2/c,cell parameters: a =18.0051(17) ?, b = 15.1660(14) ?, c = 25.680(2) ?, α= 90°,β =106.041(2)°, γ = 90°, Z = 4,V = 6739.3(10) ?3, R1 = 0.0681(2997), w R2 = 0.1387(5928);Complex 3: empirical formula: C48H64Co6N4O26·2Me OH, Mr: 1530.70, Monoclinic, space group: C2/c, cell parameters: a =17.9738(8) ?, b = 15.0717(8) ?, c = 24.5022(14) ?, α= 90°,β = 102.627(5)°, γ = 90°,Z = 4,V = 6477.0(6) ?3, R1 = 0.0504(4888), w R2 = 0.1227(6381).Finally, the antimicrobial activity studies of Gram-positive/negative bacteria were also performed upon the mentioned compounds above. |
PDF Full Text Request