含不同芳香取代基的肼基二硫代甲酸甲酯-Ga3+配合物的合成及抑菌活性

设计合成了4种含不同芳香取代基团的肼基二硫代甲酸甲酯配体（2-乙酰基吡啶肼基二硫代甲酸甲酯（L¹-H）、2-甲酰基吡啶肼基二硫代甲酸甲酯（L²-H）、2-甲酰基噻吩肼基二硫代甲酸甲酯（L³-H）、2-甲酰基水杨醛肼基二硫代甲酸甲酯（L⁴-H））的镓配合物,对它们的抑菌活性进行了测试,并讨论了配体分子中不同芳香取代基对配合物抑菌活性的影响。在模拟生理条件下,L与Ga³⁺生成较稳定的单核配合物[Ga（L¹）₂]NO₃（1）、[Ga（L²）₂]NO₃（2）、[Ga（L³）₂]NO₃（3）、[Ga（L⁴）₂]NO₃（4）,各配合物对金黄色葡萄球菌和大肠杆菌表现出比Ga（NO₃）₃·9H₂O强的抑制活性,抑制金黄色葡萄球菌的能力高于大肠杆菌,其中,1和2的活性比相应配体高,其余2个配合物与其配体之间无明显活性差异。L¹和L²分子中吡啶基的较强吸电子效应可能是1和2具有较强抑菌活性的主要原因。4种配合物抑制黑曲霉生长的活性同样高于Ga（NO₃）₃·9H₂O,其中3最强,并显著高于L³,其余配合物与相应配体间无活性差异。     

IR and <Superscript>31</Superscript>P NMR spectroscopic study of complexation of carbamoyl methyl phosphinates with U<Superscript>VI</Superscript> and Th<Superscript>IV</Superscript> in nitric acid solutions

The composition of complexes formed upon the extraction of U^VI and Th^IV nitrates with O-n-nonyl(N,N-dibutylcarbamoylmethyl) methyl phosphinate (L) from solutions of nitric acid without additional solvent was determined by ³¹P NMR spectroscopy. The structures of the complexes formed were studied by IR spectroscopy. Uranium(VI) is extracted from 3 and 5 M solutions of HNO₃ as the [UO₂(L)₂(NO₃)₂] complex, while thorium(IV) is extracted from 5 M HNO₃ as the [Th(L)₃(NO₃)₃]⁺·NO ₃ ⁻ complex. In both cases, ligand L has bidentate coordination. Ligand L contacts with 3 and 5 M nitric acid to form adducts L·HNO₃ and L· (HNO₃)₂, respectively. Published in Russian in Izvestiya Akademii Nauk. Seriya Khimicheskaya, No. 11, pp. 2460–2464, November, 2005.     

Cu(II) complexes with chiral ethylenediaminodioxime and propylenediaminodioxime, the derivatives of monoterpenoid α-pinene: Synthesis and structures

Copper(II) complexes with chiral ethylenediaminodioxime (H₂L¹) and propylenediaminodioxime (H₂L²), the derivatives of terpenoid α-pinene, of the composition [Cu(H₂L¹)](NO₃)₂ (I) and [Cu(H₂L²)NO₃]NO₃ (II) are synthesized and studied by X-ray diffraction method. The ionic structures of I and II consist of complex cations [Cu(H₂L¹)]²⁺ (I), [Cu(H₂L²)NO₃]⁺ (II), and outer-sphere anions NO ₃ ^? . In the cation of compound I, the Cu²⁺ ion (C.N.4) coordinates four N atoms of tetradentate cycle-forming ligand H₂L¹ with anti-configuration. The coordination surrounding of the Cu atom is a trapezoidally distorted square. In the cation of compound II, the Cu²⁺ ion (C.N.5) coordinates the O atom of monodentate nitro group in addition to four N atoms of tetradentate cycle-forming ligand H₂L². The coordination polyhedron of the Cu atom has the shape of a distorted square pyramid N₄O. Coordinated H₂L² molecule has amphi-configuration, which is responsible for the formation of hydrogen bond between the oxime groups. The complex cations and NO ₃ ^? anions in structures I and II are linked into ionic ensembles by hydrogen bonds.     

含不同芳香取代基的肼基二硫代甲酸甲酯-Ga~(3+)配合物的合成及抑菌活性

设计合成了4种含不同芳香取代基团的肼基二硫代甲酸甲酯配体(2-乙酰基吡啶肼基二硫代甲酸甲酯(L1-H)、2-甲酰基吡啶肼基二硫代甲酸甲酯(L2-H)、2-甲酰基噻吩肼基二硫代甲酸甲酯(L3-H)、2-甲酰基水杨醛肼基二硫代甲酸甲酯(L4-H))的镓配合物,对它们的抑菌活性进行了测试,并讨论了配体分子中不同芳香取代基对配合物抑菌活性的影响。在模拟生理条件下,L-H与Ga3+生成较稳定的单核配合物[Ga(L1)2]NO3(1)、[Ga(L2)2]NO3(2)、[Ga(L3)2]NO3(3)、[Ga(L4)2]NO3(4),各配合物对金黄色葡萄球菌和大肠杆菌表现出比Ga(NO3)3·9H2O强的抑制活性,抑制金黄色葡萄球菌的能力高于大肠杆菌,其中,1和2的活性比相应配体高,其余2个配合物与其配体之间无明显活性差异。L1-H和L2-H分子中吡啶基的较强吸电子效应可能是1和2具有较强抑菌活性的主要原因。4种配合物抑制黑曲霉生长的活性同样高于Ga(NO3)3·9H2O,其中3最强,并显著高于L3-H,其余配合物与相应配体间无活性差异。     

Extraction and extraction chromatographic separation of minor actinides from sulphate bearing high level waste solutions using CMPO

Bench-Scale studies on the partitioning and recovery of minoractinides from the actual and synthetic sulphate-bearing high level waste (SBHLW) solutions have been carried out by giving two contacts with 30% TBP to deplete uranium content followed by four contacts with 0.2M CMPO+1.2M TBP in dodecane. The acidity of the SBHLW solutions was about 0.3M. In the case of actual SBHLW, the final raffinate contained about 0.4% -activity originally present in the HLW, whereas with synthetic SBHLW the -activity was reduced to the background level.¹⁴⁴Ce is extracted almost quantitative in the CMPO phase,¹⁰⁶Ru about 12% and¹³⁷Cs is practically not extracted at all. The extraction chromatographic column studies with synthetic SBHLW (aftertwo TBP contacts) has shown that large volume of waste solutions could be passed through the column without break-through of actinide metal ions. Using 0.04M HNO₃>99% Am(III) and rare earths could be eluted/stripped. Similarly >99% Pu(IV) and U(VI) could be eluted.stripped using 0.01M oxalic acid and 0.25M sodium carbonate, respectively. In the presence of 0.16M SO ₄ ^2– (in the SBHLW) the complex ions AmSO ₄ ⁺ , UO₂SO₄, PuSO ₄ ²⁺ and Pu(SO₄)₂ were formed in the aqueous phase but the species extracted into the organic phase (CMPO+TBP) were only the nitrato complexes Am(NO₃)₃·3CMPO, UO₂(NO₃)₂·2CMPO and Pu(NO₃)₄·2CMPO. A scheme for the recovery of minor actinides from SBHLW solution with two contacts of 30% TBP followed by either solvent extraction or extraction chromatographic techniques has been proposed.     

Macrocyclic effects upon isomeric CuIIMII and MIICuII cores. Formation with unsymmetric phenol-based macrocyclic ligands

This paper discusses coordination-position isomeric M^IICu^II and Cu^IIM^II complexes, using unsymmetric dinucleating macrocycles (L^m;n)²⁻ ((L^2;2)²⁻, (L^2;3)²⁻ and (L^2;4)²⁻) that comprise two 2-(N-methyl)-aminomethyl-6-iminomethyl-4-bromo-phenonate entities, combined through the ethylene chain (m = 2) between the two amine nitrogens and through the ethylene, trimethylene or tetramethylene chain(n = 2, 3 or 4) between the two imine nitrogens. The macrocycles have dissimilar N(amine)₂O₂ and N(imine)₂O₂ metal-binding sites sharing the phenolic oxygens. The reaction of the mononuclear Cu^II precursors, [Cu(L^2;2)], [Cu(L^2;2)] and [Cu(L^2;2)], with a M^II perchlorate and a M^II acetate salt formed (acetato)M^IICu^II complexes: [CoCu(L^2;2)(AcO)]ClO⁴·0.5H₂O] (1), [NiCu(L^2;2) (AcO)]ClO₄ (2), [ZnCu(L^2;2) (AcO)]ClO₄ (3), [CoCu(L^2;3)(AcO)]ClO₄·0.5H₂O (4), [NiCu(L^2;3)(AcO)]ClO₄ (5), [ZnCu(L^2;3)(AcO)]ClO₄·0.5H₂O (6), [CoCu(L^2;4)(AcO)(DMF)]ClO₄ (7), [NiCu(L^2;4) (AcO)]ClO₄·2DMF (8) and [ZnCu(L^2;4)(AcO)]ClO₄ (9) (the formulation [M_aM_b (L^m;n)]²⁺ means that M_a resides in the aminic site and M_b in the iminic site). The site selectivity of the metal ions is demonstrated by X-ray crystallographic studies for 2·MeOH,3,5,7, and9. An (acetato)Cu^IIZn^II complex, [CuZn(L^2;3)(AcO)]ClO₄ (10), was obtained by the reaction of [PbCu(L^2;3)]-(ClO₄)₂ with ZnSO₄·4H₂O, in the presence of sodium acetate. Other complexes of the Cu^IIM^II type were thermodynamically unstable to cause a scrambling of metal ions. The Cu migration from the iminic site to the aminic site in the synthesis of10 is explained by the ‘kinetic macrocyclic effect’. The coordination-position isomers,6 and10, are differentiated by physicochemical properties.     

Complexation and extraction of non-ferrous metals by calix[n]arene phosphine oxides

The extraction of non-ferrous metal (M²⁺) nitrates by the calix[4,6]arenes (L), bearing four or six phosphine oxide donor groups at the upper or at the lower rim, was quantitatively described in the form of [M_n(NO₃)_2nL] (n = 1, 2) complexes. The extraction constants (Zn²⁺ > Cu²⁺ > Co²⁺ > Ni²⁺) for the both types of L coincide with Irving-Williams sequence. Calix[4]arenes, phosphorylated at the lower (narrow) rim, provide better stability of ML complexes because of the best spatial fitting of M²⁺ by the donor groups. For the upper (wide) rim phosphorylated calix[4]arenes M₂L and ML₂ complexes are more stable. Unusual zwitterionic [Co₂(NO₃)₄L] complex of the lower rim tetraphosphorylated calix[4]arene 1 was determined by X-ray structural analysis.     

Complexation between uranyl(VI) and CMPO in a hydroxyl-functionalized ionic liquid: An extraction,spectrophotography, and calorimetry study

The extraction complexes of uranyl(VI) in HNO₃ to a hydroxyl-functionalized ionic liquid (IL) phase, HOEtmimNTf₂ bearing CMPO, were investigated. Three possibly successive extraction complexes, UO₂L²⁺ (L = CMPO), UO₂L₂²⁺ and UO₂L₃²⁺, were detected based on variable U/L ratios. Uranyl(VI) prefers to be extracted as complex UO₂L₃²⁺, combining with the ions from HOEtmimNTf₂ to construct a solid material through self-assembly. The thermodynamics of complexes, UO₂L_j²⁺ (j = 1-3), were studied by spectrophotometry and microcalorimetry. All the formation reactions are principally driven by entropy, although a small part of the driving force of complexes UO₂L₂²⁺ and UO₂L₃²⁺ comes from enthalpy. Based on the thermodynamic properties for complex UO₂L₃²⁺, we provide a possible coordination mode in HOEtmimNTf₂: the first CMPO molecule coordinates with UO₂²⁺ in a bidentate fashion while the others do in a monodentate fashion. The results offer a thermodynamic insight into the formation behaviors of the uranyl(VI)/CMPO complexes involving the special IL HOEtmimNTf₂, which is of significance to advance the novel IL extraction strategy.     

Complexes of Co(II), Ni(II), and Cu(II) with 4-(3,4-dichlorophenyl)-1,2,4-triazole

Novel oligonuclear complexes of Co(II), Ni(II), and Cu(II) with 4-(3,4-dichlorophenyl)-1,2,4-triazole (L) of the composition [M₃L₁₀(H₂O)₂](NO₃)₆ (M = Co(II), Ni(II)), [Ni₃L₆(H₂O)₆]Hal₆ (Hal = Cl^?, Br^?), and [Cu₅L₁₆(H₂O)₂](NO₃)₁₀ · 2H₂O were synthesized and studied by magnetic susceptibility, electronic and IR spectroscopy, and powder X-ray diffraction methods. All the above complexes are X-ray amorphous. Antifer-romagnetic exchange interactions between the M²⁺ ions were discovered in the [Co₃L₁₀(H₂O)₂](NO₃)₆ and [Ni₃L₁₀(H₂O)₂](NO₃)₆ complexes, whereas ferromagnetic exchange interactions were observed in the complexes [Ni₃L₆(H₂O)₆]Cl₆, [Ni₃L₆(H₂O)₆]Br₆, and [Cu₅L₁₆(H₂O)₂](NO₃)₁₀ · 2H₂O.     

Hydrogen-bonded Networks in Crown Ether Complexes of Hydrated Metal Ions

Abstract

The hydrated metal nitrates (M(NO₃)₃.6H₂O, M[dbnd]Co, Ni, Cu, Zn and Cd) have been crystallised from water in the presence of 18-crown-6 and their structures determined by X-ray crystallography. In the case of copper, a pseudo four-coordinate square planar complex resides in an extended six-coordinate octahedral array which is further bound in a single-stranded one-dimensional hydrogen bonded polymeric mode. For M[dbnd]Co,Ni,Zn and Cd isomorphous complexes are isolated where the octahedral [M(H₂O)₅(NO₃)⁺ cation resides in a two-dimensional polymeric network through hydrogen bonds between the water ligands and either the crown ether oxygens or unbound nitrate ions or water molecules.     

Cerium(IV) Nitrate Complexes With Bidentate Phosphine Oxides

The reactions between ceric ammonium nitrate, (NH₄)₂Ce(NO₃)₆, (CAN) and the bidentate phosphine oxides, 4,5-bis(diphenylphosphine oxide)-9,9-dimethylxanthene (L¹), oxydi-2,1-phenylene bis(diphenylphosphine dioxide) (L²), 1,2-bis(diphenylphosphino)ethane dioxide (L³) and 1,4-bis(diphenylphosphino)butane dioxide, L⁴ have been investigated. The crystal structures of the molecular Ce(NO₃)₄L¹ ( 1 ), and ionic [Ce(NO₃)₃L³₂][NO₃]⋅CHCl₃ ( 3 ), [Ce(NO₃)₃L³₂][NO₃] ( 4 ) and the polymeric [Ce(NO₃)₃L⁴_1.5] [NO₃] ( 5 ) and the cerium(III) complex [Ce(NO₃)₂L¹₂][NO₃] ( 2 ) are reported. The thermal stability of the complexes has been examined by thermogravimetry with the gaseous decomposition products analysed by infrared spectroscopy. Evolution of CO₂ is found for both Ce(III) and Ce(IV) complexes with the later also forming NO₂. The formation of the complexes in solution has been studied by ³¹P NMR spectroscopy and further complexes [Ce(NO₃)₃L¹₂]⁺[NO₃]⁻ and [Ce(NO₃)₂L¹₃]²⁺2[NO₃]⁻ identified in CD₃CN solution. The complex ( 1 ) exists as a single molecular species in solution and is stable in dichloromethane whilst ( 3 ) decomposes on standing in both CD₂Cl₂ and CD₃CN to Ce(III) containing species. Complexes of L² have been identified by solution ³¹P NMR spectroscopy and these decompose in solution to give Ce(NO₃)₃L²₂. This study represents the first structural characterisations of Ce(IV) complexes with bidentate phosphine oxides.     

Silver(I) complexes with halo-substituted cyanoanilines: synthesis,characterization and antibacterial activity

Four Ag(I) complexes, [Ag(L₁)₂](NO₃) (1), [Ag(L₂)(NO₃)] (2), [Ag(L₃)₃](NO₃) (3), and [Ag(L₄)₂](NO₃) (4), with ligands derived from halo-containing cyanoanilines (L₁ = 4-amino-3fluorobenzonitrile, L₂ = 4-amino-3-chlorobenzonitrile, L₃ = 4-amino-3-bromobenzonitrile, L₄ = 4-amino-2-bromobenzonitrile) were synthesized and characterized by C, H, and N elemental analysis, IR and ¹H NMR spectroscopy and single crystal X-ray diffraction. Complexes 1–4 crystallized in the triclinic space group C2/c, P2(1)/n, P-1 and C2/c, respectively. In 1 and 4, Ag⁺ is four-coordinate with L₁ or L₄ to form 1-D _∞{[Ag(L₁/L₄)₂]⁺} polymeric cations. In 2, Ag⁺ is three-coordinate by two L₂ ligands and one NO₃^? ligand to form a 1-D _∞{[Ag(L₂)(NO₃)]} zigzag chain. In 3, Ag⁺ is four-coordinate by L₃ to form a dinuclear [Ag(L₃)₃]⁺ cation. The NO₃^? is a 4-connector bridging group in 1 and 3 and a 5-connector bridging group in 2 and 4. The intermolecular hydrogen bonds and Ag?O weak interactions play important roles in forming 3-D networks of 1–4. The antibacterial activities for 1–4 were evaluated against Bacillus subtilis, Staphylococcus aureus and Escherichia coli with MTT method. The antibacterial results indicated that 2 showed the best inhibitory activity against the test bacterial strains, and was as potent as chloramphenicol.     

Extraction of heterometallic complexes of ruthenium and nonprecious metals by phosphorylmethylated calix[4]arenes from nitrate solutions

Synergetic extraction of [RuNO(NO₂)₄OH]^2? by calix[4]arene phosphine oxides (L) in the form of Ru/M heterometallic complexes was studied in the presence of nonprecious metals (M²⁺). The main extraction laws were recognized for [M(NO₃)₂L _n ] and [RuNO(NO₂)₄OH])ML _m ], where M²⁺ = Zn²⁺, Cu²⁺, Co²⁺, or Ni²⁺ and n, m = 1 or 2; extraction constants were determined for these metals. The variation row of the extraction constants with varying metal (Zn²⁺ > Cu²⁺ > Co²⁺ > Ni²⁺) coincides with the Irving-Williams row. Two or three PO groups of extractant L and the OH and NO₂ groups of the ruthenium anion are coordinated to the M²⁺ atom in Ru/M complexes. The conditions for generation of the Ru/Zn complex and its complete extraction were optimized as applied to the extraction of fission ruthenium from nitrated nitric acid and imitation solutions.     

Trigonal (-3) symmetry octahedral lanthanide(III) complexes of zwitterionic tripodal ligands: luminescence and magnetism

Sandwich coordination complexes, [Ln^III(H₃L)₂]X₃?solvents, of Tb(III), Eu(III), Dy(III), Ho(III) and Er(III) were prepared with two new zwitterionic ester-substituted tripodal amine ligands, tris((2-hydroxy-5-n-butyl benzoate)aminoethyl)-amine (H₃L¹) and tris((2-hydroxy-5-methyl benzoate)aminoethyl)-amine (H₃L²). These ligands were synthesised by condensation of the appropriately substituted salicylaldehyde with tris(2-aminoethyl)amine (tren) followed by in situ reduction of the tris-imine to tris-amine. Subsequent 2:1 reaction with lanthanide(III) ions yields [Ln^III(H₃L)₂]X₃?solvents (L = L¹, L²; X = Cl^?, NO₃^?; solvents = MeOH or H₂O). All complexes were characterised by microanalysis, infrared spectroscopy, high resolution mass spectrometry and solid-state photoluminescence measurements. The crystal structures of [Tb^III(H₃L¹)₂]Cl₃·6MeOH, [Dy(H₃L¹)₂]Cl₃·6MeOH, [Eu^III(H₃L¹)₂]Cl₃·6MeOH and [Tb^III(H₃L¹)₂](NO₃)₃ reveal high-crystallographic ?3 symmetry at the O₆-coordinated octahedral lanthanide(III) ions and that the tripodal ligands are bound in zwitterionic form: the protons from the phenolic oxygens have migrated to the amino nitrogens. Photoluminescence measurements indicate various degrees of energy transfer of the ligand chromophore to the lanthanide ions, as both ligand and lanthanide emission features are observed. Despite the high-crystallographic symmetry and the likely small transverse magnetic anisotropy of the complexes, no evidence of slow relaxation of the magnetisation, characteristic of a single-molecule magnet, was observed for [Tb^III(H₃L¹)₂]Cl₃·MeOH·3H₂O, [Dy^III(H₃L¹)₂]Cl₃·6H₂O, [Ho^III(H₃L¹)₂](NO₃)₃·2H₂O, [Er^III(H₃L¹)₂]·H₂O and [Tb^III(H₃L¹)₂](NO₃)₃ down to 2.0 K.     

Extraction of heterometal ruthenium(II) complexes by diphenyl(dibutylcarbamoylmethyl)phosphine oxide from nitrate-nitrite solutions

The synergistic extraction of [RuNO(NO₂)₄OH]^2? by diphenyl(dibutylcarbamoylmethyl)phosphine oxide (L) in the presence of nonprecious metal cations (M²⁺) is studied; the extraction occurs on the account of the formation of heterometal complexes [RuNO(NO₂)₄OHML_m] (M = Zn, Cu, Co, Ni) due to the addition of M²⁺ to ruthenium through the oxygen atoms of the OH and NO₂ groups and the bidentate coordination of L to M²⁺. The extraction constants for Ru/M complexes and ML_n(NO₃)₂ are determined. The variation in the extraction constants with changing M (Co, Zn, Cu > Ni) does not agree with the Irwing-Williams row, unlike the extraction with monodentate PO-containing extractants (Zn > Cu > Co > Ni). The feasibility of ruthenium extraction in the form of Ru/M complexes from complex nitrate-nitrite solutions is demonstrated.     

Thermochemical and spectrophotometrical study of Ni(II) Complexes with Thiadiamines

Ni(II) complexes of some linear tridentates with one sulphur and two nitrogen donors have been studied in aqueous solution at 25°C in 0.5 M (K)NO₃ medium by means of the calorimetric and spectrophotometric technique. It is shown that the percentage facial isomer in the NiL²⁺ complexes becomes more important with increasing substitution on the nitrogen or sulphur donor atoms. The NiL₂²⁺ complexes most probably have a trans-facial tetragonally distorted structure with four equatorially bound nitrogen donors and in axial position the sulphide donors. The same {Ni-(N₄S₂)}²⁺ cation was also present in the NiL₂(NO₃)₂ solid state compounds.     

Tetra-CMPO-derivatives of calix[4]arenes fixed in the 1,3-alternate conformation

Calix[4]arene derivatives fixed in the 1,3-alternate conformation and substituted at one side by four carbamoylmethylphosphine oxide (CMPO) residues were synthesised. Two CMPO groups are directly attached to the wide rim, while the second pair is bound to the narrow rim via a tri- or tetramethylene spacer. Similar compounds, in which two CMPO groups at the wide rim are combined with two picolinamide groups or two ionisable carboxylic groups at the narrow rim, were also prepared. Some of these calixarene derivatives were studied as extractants for lanthanides (La³⁺, Eu³⁺, Yb³⁺) and thorium (Th⁴⁺) from acidic solution into methylene chloride. For selected samples, stability constants in methanol were determined by spectrophotometric titrations. Three compounds (1b′, 13, 17) in the 1,3-alternate conformation and one intermediate in the cone conformation (18) were confirmed by a crystal structure.     

Synthesis,characterization, DNA-binding,and antioxidant activities of four copper(II) complexes containing N-(3-hydroxybenzyl)-amino amide ligands

Four new substituted amino acid ligands, N-(3-hydroxybenzyl)-glycine acid (HL₁), N-(3-hydroxybenzyl)-alanine acid (HL₂), N-(3-hydroxybenzyl)-phenylalanine acid (HL₃), and N-(3-hydroxybenzyl)-leucine acid (HL₄), were synthesized and characterized on the basis of ¹H NMR, IR, ESI-MS, and elemental analyses. The crystal structures of their copper(II) complexes [Cu(L₁)₂]·2H₂O (1), [Cu(L₂)₂(H₂O)] (2), [Cu(L₃)₂(CH₃OH)] (3), and [Cu(L₄)₂(H₂O)]·H₂O (4) were determined by X-ray diffraction analysis. The ligands coordinate with copper(II) through secondary amine and carboxylate in all complexes. In 2, 3, and 4, additional water or methanol coordinates, completing a distorted tetragonal pyramidal coordination geometry around copper. Fluorescence titration spectra, electronic absorption titration spectra, and EB displacement indicate that all the complexes bind to CT-DNA. Intrinsic binding constants of the copper(II) complexes with CT-DNA are 1.32?×?10^6?M^?1, 4.32?×?10^5?M^?1, 5.00?×?10^5?M^?1, and 5.70?×?10^4?M^?1 for 1, 2, 3, and 4, respectively. Antioxidant activities of the compounds have been investigated by spectrophotometric measurements. The results show that the Cu(II) complexes have similar superoxide dismutase activity to that of native Cu, Zn-SOD.     

Complexes of [(iPrO)2P(O)NHC(S)NHCH2]2CH2 with Co(II), Ni(II), Zn(II), and Pd(II): Reaction of [(iPrO)2P(O)NHC(S)NHCH2]2 with KOH Leading to the Imidazolidine-2-Imine Derivative

Reaction of O,O′-diisopropylphosphoric acid isothiocyanate (iPrO)₂P(O)NCS with NH₂(CH₂)_nNH₂ (n = 3, 2) leads to the N-phosphorylated bis-thioureas [(iPrO)₂C(S)NHP(O) NH]₂Z (Z = —(CH₂)₃—, H₂L^I ; —(CH₂)₂—, H₂L^II ). Reaction of the potassium salt of H₂L^I with Co(II) and Zn(II) in aqueous EtOH leads to complexes of formula M₂(L-O,S)₂. The metal cation in both complexes is coordinated by two deprotonated ligands through the sulfur atoms of the thiocarbonyl groups and the oxygen atoms of the phosphoryl groups. Reaction of K₂L^I with Ni(II) and Pd(II) in the same conditions leads to M₂(L-N,S)₂ complexes. In both compounds, the metal center is found in a square-planar N₂S₂ environment formed by the C=S sulfur atoms and the P—N nitrogen atoms of two deprotonated ligands L^I . Reaction of H₂L^II with KOH leads to a product of heterocyclization, in which one of the thiourea fragments is retained. Compounds obtained were investigated by IR, UV-Vis, ¹H and ³¹P NMR spectroscopy, and microanalysis.     

Electrospray Mass Spectrometry Study on Polynuclear Pd(II) and Ni (II) Complexes of 3, 6, 9, 16, 19, 22‐Hexaazatricyclo [22. 2.2.211,14] triaconta‐11, 13, 24, 26 (1), 27, 29‐Hexaene

Polynuclear Pd(II) and Ni(II) complexes of macrocyclic polyamine 3,6,9,16,19,22‐hexaazatricyclo[22.2.2.2^11,14]‐triaconta 11,13,24,26(l),27,29‐hexaene (L) in solution were investigated by electrospray ionization mass spectrometry (ESIMS). For methanol solution of complexes M₂LX₄ (M = Pd(II) and Ni(II), X= Cl and I), two main clusters of peaks were observed which can be assigned to [M₂LX₃]⁺ and [M₂LX₂]²⁺. When Pd₂LCl₄ was treated with 2 or 4 mol of AgNO₃, it gave rise formation of Pd₂LCl₂ (NO₃)₂ · H₂O and [Pd₂L(H₂O)_m(NO₃)_n]^(4‐n)+, respectively. ESMS spectra show that the dissociation of the former in the ionization process gave peaks of [Pd₂LCl₂]²⁺ and [(Pd₂LCl₂)NO₃]⁺, while dissociation of the later gave the peaks of [Pd₂L(CH₃CO₂)₂]²⁺ and [Pd₂L(CH₃CO₂)₂](NO₃) ⁺ in the presence of acetic acid. Similar species were observed for Pd₂LI₄ when treated with 4 mol of AgNO₃. When [Pd₂L · (H₂O)_m(NO₃)_n]^(4‐n)+ reacted with 2 mol of oxalate anions at 40°C, [Pd₄L₂(C₂O₄)₂(NO₃)₂]²⁺ and [Pd₄L₂(C₂O₄)₂ (NO₃)]³⁺ were detected. This implies the formation of square‐planar molecular box Pd₄L₂(C₂O₄)₂(NO₃)₄ in which C₂O₄^? may act as bridging ligands as confirmed by crystal structure analysis. The dissociation form and the stability of complex cations in gaseous state are also discussed. This work provides an excellent example of the usefulness of ESIMS in the identification of metal complexes in solution.