Synthesis and spectroscopic characterization of Zn(II), Cd(II), and Hg(II) ciprofloxacin complexes

Ciprofloxacin metal co mplexes with general for mula [M(CPF)₂]X₂·nH₂O [M = Zn(II), Cd(II), and Hg(II)] have been synthesised and characterized using elemental analysis (CHN), spectroscopic (UV-Vis, IR, MS, and ¹H NMR) and ther mogravimetric (TG and DTA) data. Using the Coats-Redfern and Horowitz-Metzeger methods, kinetic analysis of the thermogravimetric data had been performed.     

Effects of radiolysis of di(2-ethylhexyl)phosphoric acid upon the extraction of strontium(II)

The radiolysis of di(2-ethylhexyl)phosphoric acid causes deterioration of the extraction of Sr(II) at about pH 5. This effect is attributed to the main radiolysis product, mono(2-ethylhexyl)phosphoric acid. However, MEHPA shows an ability of extracting Sr(II) in an acid medium. The presence of TBP prevents MEHPA from extracting Sr(II) in acidic solutions. The decrease of Df due to γ-irradiation is almost consistent with that estimated from the G values for the decomposition of DEHPA and formation of MEHPA. The diluent effect of radiolysis on the extraction was also determined.     

Electrometric study of uranyl(II) and beryllium(II) complexes of 2,2′-dimercapto diethyl ether

Complexation of uranyl(II) and beryllium(II) ions with 2,2′-dimercaptodiethyl ether has been studied in 40% ethanolic media by potentiometric and conductometric titration techniques revealing the formation of an 1∶1 complex in either case. The stability constants of the complexes have been determined at ionic strength μ=0.1M (NaClO₄) by applyingCalvin andMelchior's extension ofBjerrum's method. LogK _stab values are found to be 12.60, 11.96 at 25 °C and 12.55, 11.90 at 35 °C respectively. The values of ΔG, ΔH and ΔS for the complexation reactions determined at 25 °C are also reported.     

Liquid-liquid extraction behaviour of mercury(II) as bromide,iodide and thiocyanate

The liquid-liquid extraction behaviour of mercury(II) as bromide, iodide and thiocyanate has been investigated in different oxygenated and non-oxygenated solvents. The effects of the molarity of acids, their sodium or potassium salts, the concentration of Hg(II) ions, the temperature and masking anions have been studied. The possibilities of separation of Hg(II) from Zn(II), Cd(II) Tl(I), Tl(II) and Au(III) in these extractions are discussed.     

Extraction of Ag(I), Cd(II), In(III), Sn(II), Sn(IV), Sb(III), and U(VI) from aqueous solutions by ketone solutions using single-step batch and continuous SISAK methods1,2

The extraction properties of Ag(I), Cd(II), In(III), Sn(II), Sn(IV), Sb(III), and U(VI) from aqueous KI/H₂SO₄ solution into a mixture of 4-methyl-2-pentanone (methyl isobutyl ketone, MIBK) and cyclohexanone (CHO) were studied. Both single-step batch and SISAK² methods were used. The oxidation of Sn(II) to Sn(IV) by iodine and complexation of Sn(IV) by 2,3-dimercapto-propanol-1 (BAL) were also investigated. A method for rapid and continuous separation of indium from tin was developed for investigation of short-lived indium fission products.     

Preparation of platinum(II) sulfide complexes immobilized on silica

We report on preparation of silica-immobilized platinum(II) complexes of the [{SiO₂}O₂Si(CH₃)· (CH₂)₃SR]₂PtCl₂ type (R = Bu, Hex, or Bn; {SiO₂} = silica surface).     

Über Reaktionen Oxygenierter Kobalt (II)-Komplexe. X. 1,4,7,10-Tetraazadecan-kobalt (II) und 4, 7-dimethyl-1,4,7,10-tetraazadecan-kobalt (II) als sauerstoffträger

Reactions of oxygenated cobalt (II) complexes. X. 1,4,7,10-tetraazadecanecobalt (II) and 4,7-dimethyl-1,4,7,10-tetraazadecanecobalt (II) as dioxygen carriers

1 IX: siehe [1].

Oxygenation of cobalt (II) chelates with fourdentate amines such as 1,4,7,10-tetraazadecane (= tad) in aqueous solution yields μ-peroxo-μ-hydroxo-dicobalt (III) complexes. Due to facultative ligand disposition of the amine, 8 different diastereoisomers are possible. Introducing methyl groups in positions 4 and 7 of tad destabilizes the isomers with β-configuration. A crystallized perchlorate, obtained by oxygenation of 4, 7-dimethyl-1,4,7,10-tetraazadecanecobalt (II) (= dmtad) in alcaline solution, proved to be of the expected μ-peroxo-μ-hydroxo type. The ligand configuration is and lattice constants a (ΔΔ/ΛΛ). The X-ray structure was solved by Patterson's method and refined to R = 0.093. The crystals are orthorhombic with space group Pna2₁ and lattice constants a = 14.632 (4), b = 17.525 (5), c = 12.888 (5) Å. In its UV./VIS. absorption spectrum and its solution reactivity the binuclear cation is closely related to oxygenation products obtained with the chelate of unsubstituted tad. The kinetic parameters of the decomposition reaction of the μ-peroxo complexes in acidic solution are compared. The binuclear cations with 4, 7-dimethyl-1,4,7,10-tetraazadecane as ligand are generally more reactive. In slightly alcaline solution isomerization of the μ-peroxo-μ-hydroxo complexes has been observed.     

Synthesis and crystal structure of zinc(II) and manganese(II) complexes of 2-(diphenylacetyl)indandione-1,3

Zinc(II) and manganese(II) complexes of 2-(diphenylacetyl)indandione-1,3 (HL) were synthesized. Crystals of [M(DMSO)₂L₂] · CHCl₃, where M= Zn^(II) (I) and Mn^(II) (II), obtained from chloroform plus dimethyl sulfoxide (DMSO) mixture were found to be isostructural based on the similarity of their unit cell parameters and unit cell volumes. The crystals are triclinic, Z = 2, space group P \(\bar 1\); a = 10.422(1) Å, b = 11.929(1) Å, c = 20.429(1) Å, α = 73.616(1)°, β = 85.095(1)°, γ = 77.586(1)° for complex I; a = 10.436(1) Å, b = 12.297(1) Å, c = 19.924(2) Å, α = 78.138(2)°, β = 87.625(2)°, γ = 82.048(2)° for complex II. X-ray structural analysis of complex I was carried out. For complex II, the structure was not refined because all of its atoms are each disordered over three to five positions. The two DMSO molecules in complex I coordinate the central metal atoms in the monodentate mode via their donor oxygen atoms to occupy an axial position and an equatorial position in an octahedral polyhedron. The other four positions are occupied by the four oxygen atoms of the two deprotonated ligands L^? coordinated in the bidentate-cyclic mode. The outer sphere of complex I contains the solvating chloroform molecule.     

Search for optimal conditions for the extraction of thiosulfate complexes of Cu(II) by 4-(5-nonyl)pyridine from aqueous mineral acid solutions

Solvent extraction of Cu(II) by 4-(5-nonyl)pyridine (NPy) in benzene from mineral acid solutions containing thiosulfate ions has been studied at room temperature (23±2°C). Mineral acid solutions alone constitute an aqueous phase from which Cu(II) is not extracted. Addition of small amounts of thiosulfate ions augments the extraction to an extent that quantitative recovery is possible. Stoichiometric studies reveal the involvement of ion-pair type complexes (NPy·H)₂·Cu(S₂O₃)₂ which are responsible for extraction. Stability constants lg K_ex for this complex are 7.2±0.2; 9.1±0.2 and 9.5±0.2 for HCl, HNO₃ and H₂SO₄, respectively. The presence of 0.01 mol/l of some complexing ions like ascorbate, acetate, citrate, oxalate, tartrate or iodide does not affect the extraction, thus allowing the recovery of the metal from diverse matrices. Under optimal conditions (0.1M NPy in benzene-0.1M HNO₃ or H₂SO₄+0.01M S₂O ₃ ^?2 or 0.5M HCl+0.05 M S₂O ₃ ^?2 ) a clean separation from some elements, e.g. Cs(I). Co(II), Fe(III), Eu(III), Ce(III), Se(IV) and Cr(VI) can be achieved.     

PET imaging of sterile inflammation with a 18F-labeled bis(zinc(II)-dipicolylamine) complex

Small-molecular probe ¹⁸F-labeled bis(zinc(II)-dipicolylamine) complex (¹⁸F-FB-DPAZn2) was evaluated for PET imaging of sterile inflammation. In comparison with ¹⁸F-2-deoxy-β-d-glucose (¹⁸F-FDG), ¹⁸F-radiolabeled Annexin V (¹⁸F-FB-Annexin V) showed rapid clearance of radioactivity from the kidney and low uptake in most tissues. Both the lower radioactivity accumulation in brain and heart and the higher uptakes in the lung, liver, and intestine were observed for the biodistribution of ¹⁸F-FB-DPAZn2. In PET imaging, ¹⁸F-FDG showed significantly higher tumor and inflammation uptake than did of ¹⁸F-FB-DPAZn2 and ¹⁸F-FB-Annexin V in the S-180 fibrosarcoma mouse model and sterile inflammation mouse model. Both ¹⁸F-FB-DPAZn2 and ¹⁸F-FB-Annexin V performed the specifically localization in inflammation, and the ratios of inflammatory lesion-to-muscle and tumor-to-muscle were 1.83 ± 0.20 and 0.90 ± 0.12 (P < 0.05) for ¹⁸F-FB-DPAZn2, and 1.51 ± 0.14 and 1.21 ± 0.12 (P > 0.05) for ¹⁸F-FB-Annexin V, respectively. Terminal deoxynucleotide end-labeling (TUNEL) assays performed on the dissected tissues showed the significantly more TUNEL-positive nuclei in the inflammatory muscle than in tumor and normal muscle, and these TUNEL results correlated with the uptake of ¹⁸F-FB-DPAZn2 in dissected tissues. Biodistribution and PET imaging studies showed that the ¹⁸F-FB-DPAZn2 is suitable for imaging sterile inflammation in vivo and is capable of the differentiating tumor from inflammation.     

Extraction of cobalt(II) with 7-(1-decenyl)-8-quinolinol into chloroform

Extraction of cobalt(II) with 7-(1-decenyl)-8-quinolinol (HRql) into chloroform was examined. The best cobalt extraction occurs in the pH region 5.5–9. In this region several other cations are extracted. The values of K_ex and pH_0.5 for cobalt extraction were found to be ?8.6 and 3.19 respectively. The composition of the extracted complex was found to be Co(Rql)₃. Cobalt is poorly reextracted from Co-HRql complex into the aqueous phase, the best results were obtained using HCl as a stripping agent.     

Synthesis and thermal properties of aminopyrimidine Ge(II) precursors for CVD/ALD technology

Derivatives of aminopyrimidine had been used as ligands in various metals complexes but not as precursors for PRAM. A series of aminopyrimidine Ge(II) precursors has been synthesized for the first time. The diamine germanium (II) precursors were tested by TG and demonstrated excellent volatilization.     

Bromo dimethyl sulfoxide osmium(II) complexes. Molecular structure of cis,fac-[OsBr2(dmso-S)3(dmso-O)]

Bromo dimethyl sulfoxide osmium(II) complexes were synthesized: trans-[OsBr₂(dmso-S)₄] (1) was obtained by the reaction of K₂[OsBr₆] with DMSO in the presence of SnBr₂ at 100°C and cis,fac-[OsBr₂(dmso-S)₃(dmso-O)] (2) was prepared by thermal isomerization of 1 in a DMSO solution at 150°C. The coordination mode of DMSO molecules was determined by IR and ¹H and ¹³C NMR spectroscopy. X-ray diffraction analysis showed that compound 2 crystallizes in the monoclinic system, space group P2₁/n; a = 8.4711(5) Å, b = 27.7876(15) Å, c = 8.5569(5) Å, β = 115.7110(10)°; Z = 4. The coordination polyhedron of osmium is a distorted octahedron; the osmium environment is formed by two cis-arranged bromine atoms and three fac-S-coordinated and one O-coordinated DMSO molecules. The interconversion of complexes in solutions was studied by UV/Vis and ¹H and ¹³C NMR spectroscopy. In chloroform and DMSO, complex 2 isomerizes to cis-[OsBr₂(dmso-S)₄] and (in the light) to 1. The complexes trans-[OsX₂(dmso-d₆)₄], where X = Cl, Br, were isolated from DMSO-d ₆ and characterized by the IR spectra.     

Synthesis and characterization of some new Cd(II) and Zn(II) macrocyclic Schiff base complexes derived from cyclocondensation of three new linear aromatic (N4) amines and 2,6-diacetylpyridine. Crystal structure and biological activity studies

Six new Cd(II) and Zn(II) macrocyclic Schiff base complexes from cyclocondensation of 2,6-diacetylpyridine and three different liner aromatic amines have been investigated. The resulting ligands, L¹ and L² are 17- and L³ 18-membered pentaaza macrocycles. The complexes have been characterized by a variety of methods such as IR, elemental analysis, EI-Mass and conductivity measurements and in the case of cadmium complex by ¹H and ¹³C NMR spectroscopy. The crystal structure of [CdL¹(CH₃OH)](ClO₄)₂ has been determined. In this complex, the Cd(II) ion is coordinated to five nitrogen donor atoms of the ligand and one oxygen atom from methanol in a N₅O environment. The geometry around the cadmium can be better described as in a slightly distorted pentagonal-pyramidal. The synthesized compounds have antibacterial activity against the three gram-positive bacteria: S. aureus, B. cereus and C. xerosis, and also against the three gram-negative bacteria: E. coli, K. pneumoniae and P. vulgaris. The results show that the antibacterial activity of cadmium complexes is greater than that of zinc complexes.     

Insight on thermal,spectral, magnetic and biological behaviour of new Ni(II), Cu(II) and Zn(II) complexes with a pentaazamacrocyclic ligand derived from nicotinamide

New species of type [MLCl₂]·nH₂O (M:Ni, n = 0; M:Cu, n = 1 and M:Zn, n = 0; L: 1,3,5,8,11-pentaazacyclotridecane-3-yl-(pyrid-3-yl)-methanone resulted by N,N’-bis(2-aminoethyl)ethane-1,2-diamine, nicotinamide and formaldehyde) were synthesised by one-pot condensation. Chemical analysis, ESI–MS, IR, ¹H NMR, ¹³C NMR, UV–Vis–NIR, EPR spectroscopy as well as magnetic data at room temperature were used in order to characterise the compounds. The data provided by IR, ESI–MS and NMR spectra are consistent with the macrocycle formation. Electronic spectra indicate that both Ni(II) and Cu(II) adopt an octahedral stereochemistry data furthermore confirmed by magnetic moments and EPR spectrum at room temperature. The electrochemical behaviour of the compounds was investigated by cyclic voltammetry. Processes as water and chloride elimination as well as oxidative degradation of the macrocyclic ligand were observed by simultaneously TG–DTA measurements. The final residue as the most stable metallic oxide was identified by X-ray powder diffraction. The compound [CuLCl₂]·H₂O (2) exhibits fungicidal and anti-biofilm activity on Candida albicans strains. The complexes exhibit a low cytotoxicity on HEp 2 cells, except for Cu(II) species that induce the cellular cycle arrest in the G2/M phase.     

Crystal structure and spectral characteristics of Bis(1-adamantyl acetoacetato)copper(II)

The structure of a new complex bis(1-adamantyl acetoacetato)copper(II) was studied by X-ray crystallography, electronic absorption spectroscopy in the visible, and vibrational spectroscopy. Copper atoms have a square coordination in both solutions and crystals. The crystals are triclinic, space group P \(\bar 1\), a = 6.9389(6) Å, b = 9.0697(8) Å, c = 11.4280(10) Å, α = 109.279(4) °, β = 100.179(4)°, γ = 98.171(4)°, V = 652.45(10) ų, Z = 2. Molecules form the crystals only due to van der Waals forces, because Cu-C intermolecular interactions, which are characteristic of other β-dicarbonyl complexes of copper(II), are absent.     

Crystal and molecular structure of (hexafluoroacetylacetonato) (pivaloylacetonato)copper(II)

The crystal structure of (hexafluoroacetylacetonato)(pivaloylacetonato)copper(II) has been determined. Crystal data for CuO₄C₁₃H₁₄F₆: a = 8.288(2) Å, b = 8.682(2) Å, c = 12.307(2) Å; α = 90.75(3)°, β = 94.29(3)°, γ = 106.60(3)°; V = 845.7(3) ų, space group \(P\overline 1 \), Z = 2, d_calc = 1.617 g/cm³. The coordination polyhedron of the copper atom is formed by four oxygen atoms of two different β-diketonate ligands with Cu-O distances within 1.874–1.946 Å; the O-Cu-O bond angles are 94.8° and 90.6°. The complexes are united into centrosymmetrical “dimers” with Cu...Cu distances of 4.365 Å.     

Influence of the bridging coordination of DMSO on the exchange interaction character in the binuclear copper(II) complex with the nonsymmetrical exchange fragment

The binuclear copper(II) complex [Cu₂L(CH₃COO)] (I), where L^3? is the azomethine trianion based on 3-methyl-4-formyl-1-phenylpyrazol-5-one and 1,3-diaminopropan-2-ol, and its DMSO adduct (II) in which the DMSO molecule acts as an additional bridging ligand are synthesized. The structure of complex II is determined by X-ray diffraction analysis, and the structure parameters of the coordination unit of complex I are determined by EXAFS spectroscopy. The μ²-coordination of the DMSO molecule in compound II results in a change in the sign of the exchange interaction parameter. In complex I, the antiferromagnetic exchange interaction (2J = ?169 cm^?1) occurs between the copper(II) ions. The exchange interaction of the ferromagnetic type (2J = 174 cm^?1) is observed in complex II. The quantum-chemical calculations of the magnetic exchange parameters by the density functional theory method show that the role of the DMSO molecule as a switch of the exchange interaction character is exclusively the stabilization of the “broken” conformation of the metallocycles.     

Reaction of copper(II) cysteinate with thiosemicarbazide: Crystal structure of a complex of copper(II) thiocyanate with thiosemicarbazide

The reaction of copper(II) cysteinate with thiosemicarbazide (TSC) in water was found to yield complex of copper(II) thiocyanate of the [Cu(TSC)₂(SCN)₂] composition, whose crystal structure was determined by X-ray crystallography. Crystals of the complex are triclinic with a = 6.040 Å, b = 7.112 Å, c = 8.276 Å, α = 91.34°, β = 101.72°, Γ = 114.83°, Z = 2, space group \(P\bar 1\). Structural units of the complex are [Cu(TSC)₂]²⁺ centrosymmetric cations and (SCN)^? anions linked by hydrogen bonds (HB), as well as by electrostatic and π-π stacking interactions. The coordination polyhedron of Cu atoms is a square completed to bipyramid; the bonds Cu(1)-N(3), Cu(1)-S(1), and Cu(1)-S(2) are 2.002 Å, 2.303 Å, and 3.015 Å, respectively.     

Studies in nickel(IV) chemistry. Kinetics of the Cu(II) ion-mediated acid decomposition of tris(dimethylglyoximato) nickelate(IV) in aqueous acidic medium

Kinetics of the Cu(II) ion-mediated acid decomposition of tris (dimethylglyoximato)nickelate(IV), Ni(dmg)₃^2? (dmg^2? = dimethylglyoximate dianion), are reported in aqueous medium in the range of 3.6 ? pH ? 6.6 at 35°C and μ = 0.57 M. The pseudo-first-order rate constants of the disappearance of Ni(IV) k_obs(M) satisfy the equation where k_ad refers to the pseudo-first-order rate constants for the proton-assisted decomposition of the Ni(IV) complex determined independently and is a function of [H⁺], and k_dec(M) to that for the Cu(II) ion-mediated route and is a function of [H⁺] and [Cu²⁺]. Both k_obs(M) and k_dec(M) are found to increase with increasing [Cu(II)]₀, tending to attain limiting values at higher relative [Cu(II)]₀. At low [Cu(II)]₀ the k_dec(M) is found to register a decrease with increasing pH in the pH range of 3.6–4.4, then an increase in the range of 4.4–5.76, and again a decrease in the range of 5.76–6.6. Results on the Cu(II) ion-mediated acid decomposition are interpreted in terms of a probable mechanism involving pH-dependent adduct formation equilibria involving the one-protonated and the two-protonated species of Ni(IV) and the various species of Cu(II) ion in the media, followed by rate-determining acid decomposition of the adduct(s) to give Ni(II) aq. and Cu(dmgH)₂. While the two-protonated Ni(IV) complex apparently reacts about five orders of magnitude faster than the one-protonated species, the aquacopper(II) reacts about two orders of magnitude slower than the hydroxoaquacopper(II).