| Transition metal complexes of salamo ligands and their analogues are the most importantcompounds with various properties. In many reactions, Salamo transition metal compoundsshow catalytic activity such as the ring opening of epoxides, the synthesis of cyclopropaneand aziridine derivatives, and so on. Many of these complexes are oxygen carriers, therefore,they can be used as models of metalloproteins. Some of these complexes possess interestingmagnetic properties. In addition, they can be utilized for analytical purposes and opticalmaterials because of their fluorescent properties. In particular, these complexes can be used asbiological models in biological chemistry. It is very useful for understanding the structures ofbiological molecules and some biological process.The syntheses of asymmetric Salamo-type ligands have drawn many attentions in thedevelopment of inorganic chemistry and stereochemistry. The asymmetric configuration canafford much more structural variations, change characteristics of previous complexesdrastically and lead to novel properties. Chemical modifications of these complexes,introduction of some functional groups or substitution of some parts with appropriate ones areeffective and inevitable. Therefore, it makes good sense to study on the new asymmetricSalamo-type compounds.In this thesis,1,2-bis(amniooxy)ethane and2,3-dihydroxybenzene-1,4-dicarbaldehydehave been synthesized. Futhermore, four Salamo-type ligands have been designed andsynthesized based on2,3-dihydroxybenzaldehyde, and five single crystals of Cu(II) and Co(II)complexes are obtained.H4L1, H6L2, H2L3, H3L4and their Cu(II) and Co(II) complexes were structurallycharacterized by melting point determination, elemental analyses, IR spectra analyses and UVspectra analyses, etc. The single crystals of the Cu(II) and Co(II) complexes and theintermolecular interactions have also been determined by X-ray crystal diffraction.[Cu2(L3)2]·CH2Cl2and [Co(L3)(H2O)2] have been synthesized by the reaction ofasymmetrical ligand H2L3with copper(II) acetate monohydrate and cobalt(II) acetatetetrahydrate in dichloromethane/ethanol.[{Co(L4)(EtOH)}2Co(H2O)]·EtOH and [{Co(L4)(n-PrOH)}2Co(H2O)]·n-PrOH have beensynthesized by the reaction of asymmetrical ligand H3L4with cobalt(II) acetate tetrahydrate indichloromethane/ethanol and dichloromethane/n-propanol, respectively.The reaction of asymmetrical ligand H3L4with copper(II) acetate monohydrate lead tothe cleavage of the N-O bond so that a new copper(II) complex [Cu2(L5)2] with the ligandH2L5was obtained.The main crystal data are listed as following: [Cu2(L3)2]·CH2Cl2: Empirical formula, C35H30Cl6Cu2N4O10, Formula weight,1006.40,Orthorhombic, P2(1)2(1)2, Unit call dimensions: a=15.1589(15), b=10.6415(12), c=12.1786(13), Z=2, V=1964.6(4)3, R1=0.0451, wR2=0.0919;[Co(L3)(H2O)2]: Empirical formula, C17H18Cl2CoN2O7, Formula weight,492.16,Monoclinic, C2/c, Unit call dimensions: a=24.780(2), b=10.5561(9), c=7.6950(5),β=107.051(2)°, Z=4, V=1924.4(3)3, R1=0.066, wR2=0.1343;[{Co(L4)(EtOH)}2Co(H2O)]·EtOH: Empirical formula, C42H54Co3N4O16, Formulaweight,1047.68, Monoclinic, P2(1)/n, Unit call dimensions: a=13.8354(14), b=17.7149(16), c=19.5607(17), β=98.9710(10)°, Z=4, V=4735.5(8)3, R1=0.0669,wR2=0.1695;[{Co(L4)(n-PrOH)}2Co(H2O)]·n-PrOH: Empirical formula, C45H60Co3N4O16, Formulaweight,1089.76, Monoclinic, P2(1)/c, Unit call dimensions: a=14.4520(13), b=17.9201(16), c=22.938(2), β=121.351(2)°, Z=4, V=5073.2(8)3, R1=0.0452, wR2=0.0584;[Cu2(L5)2]: Empirical formula, C22H26Cu2N2O8, Formula weight,573.53, Monoclinic, P2(1)/c, Unit call dimensions: a=16.7483(19), b=11.5224(11), c=12.7770(13), β=108.257(2)°, Z=4, V=2341.6(4)3, R1=0.0653, wR2=0.1512;... |
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