Mono- and dinuclear silver(I) complexes of benzene- and pyridine-bearing 20-membered thiaoxaaza macrocycles

Two 20-membered penta- and hexadentate macrocycles containing one or two pyridine subunits, namely [20]aneNO₂S₂ (L¹) and [20]aneN₂O₂S₂ (L²), have been synthesized. Reaction of L¹ with silver(I) nitrate afforded a unique 2:2 (M:L) disilver(I) complex [μ₂-Ag₂(L¹)₂](NO₃)₂ (1) in which two four-coordinate Ag atoms bridge two ligands to form a cyclic dimer. In contrast, an endo-dentate 1:1 monosilver(I) complexes [AgL²]X; [X = ClO₄ (2) or PF₆ (3)] which show isomorphous structures were obtained from the reactions of L² with silver(I) salts.     

Dicyanamido-metal(II) complexes. Part 5: First example for a unit cell containing dinuclear and 1-D polymeric Cu(II) complexes bridging by dicyanamide

The reaction of Cu(ClO₄)₂, N,N,N′,N″,N″-pentamethylethylenetriamine (pmedien) and sodium dicyanamide (Nadca) in aqueous medium led to the isolation of {[Cu(pmedien)(μ_1,5-dca)]₂(ClO₄)₂,[Cu(pmedien)(μ_1,5-dca)]_n(ClO₄)_n} (1). The complex was structurally and magnetically characterized. Single X-ray crystallography for 1 reveals the existence of two independent molecules in the unit cell: dinuclear doubly bridging complex and a 1-D polymeric chain with dca in both cases acting as a μ_1,5-bridging ligand via the terminal nitrile nitrogen atoms. Magnetic susceptibility measurements of the complex showed that the Cu(II) ions are weakly coupled with ferromagnetic interaction in the dinuclear unit (J_d = 0.9 cm^–1) and antiferromagnetic interaction in the polymeric chain (J_c = ? 0.6 cm^? 1).     

A novel polymeric silver(I) complex with a one-dimensional chain structure

The polymeric silver(I)–thiolate complex [Ag₆(μ₃-SC₄N₂H₃)₄(μ₂-SC₄N₂H₃)₂]_n has been prepared from the assembly reaction of AgSCN and sodium pyrimidine-2-thiolate in DMF. X-ray diffraction analyses show that the complex exhibits a one-dimensional chain structure with the metal atom core arranged in distorted tetrahedra sharing apexes. The pyrimidime-2-thiolate ligands in the chain act as both bridging and chelating ligands linking either two- or three-silver(I) centers. The coordination environment of each Ag(I) in the complex is either a distorted tetrahedron of S₃N or a triangle of S₂N.     

Helical metallomacrocyclic nickel(II) complexes of a tetradentate N2S2 ligand derived from N-methyldithiocarbazic acid

The structure of the tetradentate sulphur–nitrogen chelating agent, 1,2-phenylenebis(methylene) bis(1-methylhydrazinecarbodithioate) (NSSN) has been determined by X-ray diffraction. In the solid state, the two arms of the ligand remain in E configurations about the hydrazinic C–N bonds. The ligand reacts with hydrated nickel(II) salts in a 3:2 ligand-to-metal ratio yielding dimeric triple helical complexes of general formula, [Ni₂(NSSN)₃]X₄·nH₂O (X = Cl, Br, I, NCS; n = 5, 6, 9) which contain two nickel(II) ions in distorted octahedral environments. An X-ray crystallographic structure determination of the [Ni₂(NSSN)₃]Cl₄·9H₂O complex shows that it is a metallomacrocycle in which each ligand acts as a bis-bidentate chelating agent providing NS donors of one arm to one nickel(II) ion and NS donors of the second arm to a second nickel(II) ion. Each nickel(II) ion adopts a distorted octahedral geometry with a NiN₃S₃ coordination core as shown by their common electronic spectra.     

1-Amino-4-aryl-2(1H)-pyrimidinthione: Acidität und Komplexbildung mit Mn(II), Co(II), Ni(II), Zn(II), Cd(II), Pb(II) und Ag(I)

1-Amino-4-aryl-2(1H)-pyrimidinethiones: Acidity and Complex Formation with Nonferrous Metal Ions and Ag(I) Acid dissociation constants of new 2, 3 and already known 1 substituted 1-amino-4-aryl-2(1H)-pyrimidinethiones and stability constants of their nonferrous metal ion and silver complexes have been measured pH-potentiometrically in a 75% (v/v) mixture of dioxane/water. The influence of the substituents on pK_a- and lgβ_n-values is discussed. The X-ray structure analysis of bis[1-(4-toluenesulfonamido)-4-(4-tolyl)-2(1H)-pyrimidinethionatol]-nickel(II) 5 proves that pyrimidinethiones coordinate via their thione sulphur and aminonitrogen. However, the bond lengths are not levelled in the chelating ring.     

Copper (II) and silver (II) complexes of polymer-bound porphyrins with Schiff base linkage

Two percent divinylbenzene (DVB)–crosslinked polystyrene was prepared and functionalized to obtain its aldehyde analog. Amino porphyrins were anchored on this polymer support by Schiff base condensation. The anchoring positions were adjusted so as to obtain ortho-, meta-, and para-isomeric systems. The polymer-bound free-base porphyrins were metallated to obtain the corresponding Cu(II) and Ag(II) complexes by treating them with the corresponding metal salt solutions. The products were characterized chemically and spectroscopically. Electronic and ESR spectral analysis shows the microenvironmental participation of the polymer network on the electronic levels of the porphyrin system. The extents of steric and electronic participation were evaluated and are presented. © 1998 John Wiley & Sons, Inc. J Appl Polym Sci 69: 89–93, 1998     

Polymer-metal complexes: Synthesis, characterization, and properties of poly(maleic acid) metal complexes with Cu(II), Co(II), Ni(II), and Zn(II)

SUMMARY Polymer metal complexes of poly(maleic acid) and Cu(II), Co(II), Ni(II), and Zn(II) were synthesized. Elemental analysis, as well as magnetic, spectral and thermal properties, in addition to electrical conductivities of the chelates were investigated, and possible structures have been assigned to the polychelates. Semi-empirical calculations at the PM3 level were carried out on the geometrical arrangement of the polychelates. Received: 19 November 1999/Revised version: 22 March 2000/Accepted: 31 March 2000     

Design and syntheses of blue luminescent Cu(II) and Zn(II) polymeric complexes with 2-(2′-pyridyl)benzimidazole derivative ligand

The polymeric complexes of 4,4′-bis[2-(2′-pyridyl)benzimidazolyl]biphenyl (Bmbp) with Cu(II) (1), Zn(II) (2) and 1,3,5-tris[2-(2′-pyridyl)benzimidazolyl]benzene (Tmb) with Cu(II) (3), Zn(II) (4) were successfully synthesized and characterized by IR spectroscopy, elemental analysis, thermal analysis and conductivity measurements. The results indicate that the stoichiometry of these metal complexes is metal: Bmbp (or Tmb) = 1:1 for 1 and 2 (2:1 for 3 and 4). Ligands coordinated with metal ions to get a five-membered chelate ring and formed polymeric complexes with metal ion. Their luminescence properties were also studied by UV–vis and fluorescence spectra. At room temperature, complexes 1–4 emit blue luminescence from 419 to 483 nm in the solid state and purple/blue luminescence from 385 to 437 nm in DMF solution. Thermal properties measurement and analysis shows that they have good thermal stabilities.     

Synthesis and characterization of polymeric complexes of cobalt(II) with chloro substituted 2-hydroxyacetophenone oximes

Summary The polymeric complexes of cobalt (II) with 5-chloro 2-hydroxyacetophenone oxime and 3,5-dichloro-2-hydroxyacetophenone oxime were synthesised and characterized by elemental analysis, magnetic measurements and spectral studies.     

Membrane Extraction of Ag(I), Co(II), Cu(II), Pb(II), and Zn(II) Ions with Di(2-Ethylhexyl)phosphoric Acid under Conditions of Electrodialysis with Metal Electrodeposition

Theoretical Foundations of Chemical Engineering - New methods for extracting cobalt and zinc ions from sulfuric acid solutions, of silver and lead ions from nitric acid solutions, and of copper...     

A new inorganic (carbon-free) chelate ring: SnO2N2. Eight-coordinated tin(IV) in Sn(O2N2Ph)4 and a self-assembled 20-membered macrocycle in [Me3Sn(O2N2Ph)]4

The reaction of cupferron (NH₄L, L=PhN(O)NO⁻) with tin(IV) and trimethyltin(IV) halides yields cupferronato complexes SnL₄ (1) and [Me₃SnL]₄ (2) which were characterised by FT-IR and FT-Raman spectroscopy. The first X-ray diffraction analysis of the complexes reveals a slightly distorted dodecahedral and trigonal-bipyramidal coordination of the central metal atoms in 1 and 2, respectively. The N-nitroso-N-phenylhydroxylaminato [PhN(O)NO⁻] ligand behaves as chelating in 1 and bridging in 2 leading to a novel five-membered chelate ring, SnO₂N₂ in 1 and an unprecedented 20-membered inorganic metallomacrocycle, Sn₄O₈N₈ in 2.     

New gold(I) and silver(I) complexes of sulfamethoxazole: Synthesis,X-ray structural characterization and microbiological activities of triphenylphosphine(sulfamethoxazolato-N2)gold(I) and (sulfamethoxazolato)silver(I)

Sulfamethoxazole (SMTZ) reacts with Ph₃PAuCl and AgCl in methanol/triethylamine to give [Ph₃PAu(SMTZ_-1H+)] (SMTZ_-1H+ = sulfamethoxazolato anion) (1) and [Ag(SMTZ_-1H+)] (2). While the lattice of 1 contains single molecules with linear N–Au–P bonds, compound 2 comprises a two-dimensional polymeric assembly of the deprotonated SMTZ ligand and silver ions, which are coordinated by one oxygen and three nitrogens in a distorted tetrahedral array. The microbiologic activities (Mueller–Hinton broth dilution tests) of 1 and 2 were determined in relation to free sulfamethoxazole.     

Alternating current chronopotentiometry—III. Electroreduction of silver(I), cadmium(II), and thallium(I) in calcium nitrate tetrahydrate melt

The electroreduction of silver(I) on a platinum electrode and of cadmium(II) and thallium(I) on a mercury electrode has been studied by alternating current chronopotentiometry. Expected relations for the diffusion controlled, one-electron deposition of an insoluble substance are obeyed for silver(I); but reduction of cadmium(II) on mercury is more complex. Nucleation of metallic thallium is the rate controlling process during the early stages of the reduction of thallium(I).     

Synthesis,structural studies,and antimicrobial activity of polymeric copper(II) tetrathiocyanato diargentate(I) complexes with some acylhydrazones

Copper(II) complexes of the type Cu[Ag(SCN)₂]₂·L (where L is acetophenone benzoyl hydrazone, acetophenone isonicotinoyl hydrazone, acetophenone salicyloyl hydrazone, acetophenone anthraniloyl hydrazone, p‐hydroxyl acetophenone benzoylhydrazone, p‐hydroxyl acetophenone isonicotinoyl hydrazone, p‐hydroxyl acetophenone salicyloyl hydrazone, or p‐hydroxyl acetophenone anthraniloyl hydrazone) were synthesized and characterized. All the complexes were polymeric and insoluble in common organic solvent and were nonelectrolytes. The ligands were coordinated through >C?O and >C?N? groups. All the SCN groups present in the complexes acted as bridges between two metal centers, resulting in a polymeric structure of the Lewis acid Cu[Ag(SCN)₂]₂ as well as its complexes. Electronic and electron spin resonance spectra suggested a square planar geometry for the Lewis acid and an elongated tetragonally distorted octahedral geometry for all the complexes. The powder X‐ray diffraction parameters for acetophenone salicyloyl hydrazone and p‐hydroxyl acetophenone anthraniloyl hydrazone complexes corresponded to orthorhombic and tetragonal crystal lattices, respectively. The complexes showed a fair degree of antifungal activity against Rizoctonia sp., Aspergillus sp., and Stemphylium sp. and moderate antibacterial activity against Clostridium sp. (Gram‐positive) and Pseudomonas sp. (Gram‐negative). The complexes were more active than the parent ligands. © 2008 Wiley Periodicals, Inc. J Appl Polym Sci, 2008