Substituted hydrazones as tridentate chelating agents

The compositions and stabilities of the metal chelates of two new tridentate ligands, pyridinc-2-aldehyde-2-quinolylhydraxonc and pyridinc-2-aldehyde-2-thiazo-lylhydrazone are reported. Cationic bis-chelates, which have been reported with similar ligands, are not formed during chelation with these ligands. The copper reaction, in which both mono- and bis-chelates are formed, is discussed in detail.     

Coordination numbers of hydrated divalent transition metal ions investigated with IRPD spectroscopy

Hydration of the divalent transition metal ions, Mn, Fe, Co, Ni, Cu, and Zn, with 5-8 water molecules attached was investigated using infrared photodissociation spectroscopy and photodissociation kinetics. At 215 K, spectral intensities in both the bonded-OH and free-OH stretch regions indicate that the average coordination number (CN) of Mn(2+), Fe(2+), Co(2+), and Ni(2+) is ~6, and these CN values are greater than those of Cu(2+) and Zn(2+). Ni has the highest CN, with no evidence for any population of structures with a water molecule in a second solvation shell for the hexa-hydrate at temperatures up to 331 K. Mn(2+), Fe(2+), and Co(2+) have similar CN at low temperature, but spectra of Mn(2+)(H(2)O)(6) indicate a second population of structures with a water molecule in a second solvent shell, i.e., a CN < 6, that increases in abundance at higher temperature (305 K). The propensity for these ions to undergo charge separation reactions at small cluster size roughly correlates with the ordering of the hydrolysis constants of these ions in aqueous solution and is consistent with the ordering of average CN values established from the infrared spectra of these ions.     

Equilibrium constants for the formation of complexes between divalent metal ions and chelating agents containing nitrogen and sulfur donors

Formation constants for the Hg²⁺ complexes of 5 potentially octadentate chelating agents have been determined utilizing a mercury electrode. The ligands, which were reported in an earlier paper, are [(H₂NC₂H₄S)₂CH]₂, (H₂NC₂H₄S)₂CHCH₂CH(SC₂H₄NH₂)₂, [(H₂NC₂H₄S)₂CHCH₂]₂, (H₂NC₂H₄S)₂CH(CH₂)₃₋CH(SC₂H₄NH₂)₂ and C₆H₄[CH(SC₂H₄NH₂)₂]₂. They each have been observed to form complexes with mercuric ion in the diprotonated form, (LH₂²⁺). In addition, from pH titrations, the order of decreasing stability for complexes of these ligands with various divalent metal ions was observed to be Hg²⁺ > Cu²⁺ > Ni²⁺ > Zn²⁺ > Cd²⁺ > Co²⁺ > Mg²⁺ > Ca²⁺. Numerous problems were encountered when measurement of the formation constants with these other metal ions was attempted and only estimates of the stability constants are presented here.     

Tetracyanomanganate(II) and its salts of divalent first-row transition metal ions

The first known paramagnetic, tetrahedral cyanide complex, [Mn(II)(CN)(4)](2)(-), is formed by the photoinduced decomposition of [Mn(IV)(CN)(6)](2)(-) in nonaqueous solutions or by thermal decomposition in the solid state. In acetonitrile or dichloromethane, photoexcitation into the ligand-to-metal charge transfer band (lambda(max) = 25 700 cm(-1), epsilon = 3700 cm(-1) M(-1)) causes the homolytic cleavage of cyanide radicals and reduction of Mn(IV). Free cyanide in dichloromethane leads to the isolation of polycyanide oligomers such as [C(12)N(12)](2)(-) and [C(4)N(4)](-), which was crystallographically characterized as the PPN(+) salt C(40)H(30)N(5)P(2): monoclinic space group = I2/a, a = 18.6314(2) A, b = 9.1926(1) A, c = 20.8006(1), beta =106.176(2) degrees, Z = 4]. In the solid state Mn(IV)-CN bond homolysis is thermally activated above 122 degrees C, according to differential scanning calorimetry measurements, leading to the reductive elimination of cyanogen. The [Mn(II)(CN)(4)](2-) ion has a dynamic solution behavior, as evidenced by its concentration-dependent electronic and electron paramagnetic spectra, that can be attributed to aggregation of the coordinatively and electronically unsaturated (four-coordinate, 13-electron) metal center. Due to dynamics and lability of [Mn(II)(CN)(4)](2-) in solution, its reaction with divalent first-row transition metal cations leads to the formation of lattice compounds with both tetrahedral and square planar local coordination geometries of the metal ions and multiple structural and cyano-linkage isomers. alpha-Mn(II)[Mn(II)(CN)(4)] has an interpenetrating sphalerite- or diamond-like network structure with a unit cell parameter of a = 6.123 A (P43m space group) while a beta-phase of this material has a noninterpenetrating disordered lattice containing tetrahedral [Mn(II)(CN)(4)](2-). Linkage isomerization or cyanide abstraction during formation results in alpha-Mn(II)[Co(II)(CN)(4)] and Mn(II)[Ni(II)(CN)(4)] lattice compounds, both containing square planar tetracyanometalate centers. alpha-Mn(II)[Co(II)(CN)(4)] is irreversibly transformed to its beta-phase in the solid state by heating to 135 degrees C, which causes a geometric isomerization of [Co(II)(CN)(4)](2)(-) from square planar (nu(CN) = 2114 cm(-1), S = (1)/(2)) to tetrahedral (nu(CN) = 2158 cm(-1), S = (3)/(2)) as evidenced by infrared and magnetic susceptibility measurements. Mn(II)[Ni(II)(CN)(4)] is the only phase formed with Ni(II) due to the high thermodynamic stability of square planar [Ni(II)(CN)(4)](2)(-).     

Synthesis of some novel divalent transition metal complexes as antimicrobials

A novel series of transition metal complexes have been synthesized from the reaction of 5-((3-(methylthio)-5-(pyridin-4-yl)-4H- 1,2,4-triazol-4-ylamino)melhyl)quinolm-8-ol with transition metal salts.The structures of these compounds have been elucidated by elemental and spectral analysis.Furthermore,compounds were screened for in vitro antimicrobial activity against the representative panel of two Gram-positive and two Gram-negative bacteria and two strains of fungus.The various compounds show potent inhibitory action against test organisms.     

New 14-membered octaazamacrocyclic complexes of divalent transition metal ions with their antimicrobial and spectral studies

A novel series of macrocyclic complexes of the type [M(C₁₈H₁₄N₁₀S₂)X₂]; where M = Co(II), Ni(II), Cu(II), Zn(II) and Cd(II); X = Cl^?, NO₃^?, CH₃COO^? has been synthesized by [2+2] condensation of thiocarbohydrazide and isatin in the presence of divalent metal salts in methanolic medium. The complexes have been characterized with the help of elemental analyses, conductance measurements, magnetic measurements, electronic, NMR and infrared spectral studies. The low value of molar conductance indicates them to be non-electrolytes. On the basis of various studies a distorted octahedral geometry may be proposed for all of these complexes. These metal complexes were also tested for their in vitro antimicrobial activities against some Gram-positive bacteria viz.Staphylococcus aureus, Bacillus subtilis, and some Gram-negative bacteria Escherichia coli, Pseudomonas aeruginosa and some fungal strains Aspergillus niger, Aspergillus flavus (molds), Candida albicans, Saccharomyces cerevisiae (yeasts). The results obtained were compared with standard antibiotic: Ciprofloxacin and the standard antifungal drug: Amphotericin-B.     

Interactions of the hormone oxytocin with divalent metal ions

The interaction of the cyclic nonapeptide oxytocin (OT) with a number of alkaline earth and divalent transition metal ions (X(2+)) was examined employing mass spectrometry (MS) and ion mobility spectrometry (IMS) techniques in combination with molecular dynamics (MD) and density functional theory (DFT) calculations. Under acidic conditions it was found that OT exhibits an exceptionally strong affinity for all divalent metal ions resulting in strong [OT + X](2+) peaks in the mass spectrum. Under basic conditions only Cu(2+) and Ni(2+)-OT complexes were detected and these were singly, doubly, triply, or quadruply deprotonated. Collision-induced dissociation of the [OT - 3H + Cu](-) complex yielded exclusively C-terminal Cu(2+)-containing fragments (Cu(2+)fragment(3-)), suggesting that the Cu(2+) ligation site includes deprotonated C-terminal backbone amide nitrogen atoms and the N-terminal amino nitrogen atom in [OT - 3H + Cu](-). MD and DFT calculations indicate a square-planar complex is consistent with these observations and with experimental collision cross sections. MD and DFT calculations also indicate either an octahedral or trigonal-bipyramidal complex between Zn(2+) and OT is lowest in energy with carbonyl oxygens being the primary ligation sites. Both complexes yield cross sections in agreement with experiment. The biological impact of the structural changes induced in OT by divalent metal ion coodination is discussed.     

二茂铁基取代酰腙的一些过渡金属配合物

本文制备了两个金属有机配位体,肉桂醛二茂铁基甲酰腙(HL^1)和二[(1-肉桂酰肼基乙基)环戊二烯基]铁(H~2L^2)及它们与一些过渡金属的配合物:ML~2^1[M=Cu(II)],ML^2[(M=Cu(II)和Zn(II)],M(HL^1)~2Cl~2[M=Cd(II),Co(II)和Ni(II)],M(H~2L^2)Cl~2[M=Mn(II),Zn(II),Co(II)和Cd(II)]。这两个配位体以烯醇式与M(OAc)~2.nH~2O中心离子配位,与MCl~2.nH~2O则以酮式配位。     

Direct evidence for two interaction modes in adsorption of divalent metal ions to iminodiacetate-type chelating resins.

The adsorption curves of divalent metal ions (M2+) to an iminodiacetate(IDA)-type chelating resin (-L2-) under the condition of metal ions in excess against IDA groups clearly indicated the difference in contribution between two species. Copper and nickel are adsorbed only as [(-L)M(II)], while cadmium and calcium are adsorbed as [(-L)M(II)] and [(-LH)2M(II)]. Addition of salts may enhance the deprotonation of IDA groups, interfere with the adsorption as [(-LH)2M(II)], and yield remarkable changes in adsorption curves, depending on the metal ions.     

Preparation of a chelating sorbent based on pyridylethylated polyethylenimine for recovering transition metal ions

A method was developed for preparing a chelating amino polymer, pyridylethylpolyethylenimine with maximal degree of substitution, by polymer-analogous transformations of branched polyethylenimine in reaction with 2-vinylpyridine. The ability of cross-linked pyridylethylpolyethylenimine with the degree of substitution of 0.32 to sorb Cu²⁺, Ni²⁺, Co²⁺, Zn²⁺, Cd²⁺, Mn²⁺, and Pb²⁺ ions present simultaneously in solution was evaluated. In an ammonium acetate sorption system (pH 3.5–4.0), the sorbent selectively interacts with Cu(II) ions.     

Synthesis and spectral study of biologically active macrocyclic complexes of divalent transition metal ions

The condensation reaction of succinyldihydrazide with glyoxal in the presence of divalent metal ions (1: 1: 1) results in the formation of the complexes of type [M(C₆H₈N₄O₂)X₂], where M = Co(II), Ni(II), Cu(II), Zn(II), Cd(II) and X = Cl⁻, NO₃⁻, CH₃COO⁻. The complexes have been characterized with the aid of elemental analyses, conductance measurements and electronic, NMR, infrared spectral studies. On the basis of these studies, a six-coordinated distorted octahedral geometry in which two nitrogen and two carbonyl oxygen atoms are suitably placed for coordination toward metal ion, has been proposed for all the complexes. The complexes were tested for their in vitro antibacterial activity. Some of the complexes showed remarkable antibacterial activities against some selected bacterial strains.     

Isonitrosopropiophenone as an ambidentate chelating agent in some transition metal complexes

Summary Isonitrosopropiophenonates of cobalt(III), cobalt(II), nickel(II) and palladium(II) have been synthesised and characterised. Isonitrosopropiophenonatonickel(II) exists as green and brown varieties, the green forming mono- as well as bispyridine adducts. The brown variety is obtained after removal of base from the adducts. I.r. data of the metal chelates suggest atrans-asymmetric structure involving N and O bonding for one form and atrans-symmetric structure involving either N or O bonding of the oximino-group for the other. The former is observed exclusively with isonitrosopropiophenonates of nickel(II) while the latter is common among the other metal chelates. The low magnetic moment of the mono-adduct is ascribed to super-exchange interaction between two metal ions through oxo-bridges in the dimer. Acis-octahedral structure has been assigned to the tris(isonitrosopropiophenonato) cobalt(III) on the basis of¹H n.m.r. data. Isonitrosopropiophenone forms mixed-ligand complexes of cobalt(III) with tetradentate Schiff bases such as SALEN,N,N-ethylenebis(salicylaldimine), and SALPN,N,N-1,3-propylenebis-(salicylaldimine), where the isonitrose group bonds through the nitrogen atom. These complexes have a N,N,N,O,O,O ligand environment. The imino-nickel(II) and -palladium(II) complexes are assigned atrans-symmetric square planar structure. Characterisation of the complexes was based upon elemental analyses, conductivity and magnetic moment, and i.r.,¹H n.m.r., and electronic spectra.     

Potentiometric responses of polymeric liquid membranes based on hydrophobic chelating agents to metal ions.

The effect of hydrophobicity of acidic chelating agents as sensing materials on the potentiometric responses of polymeric liquid membranes was investigated. The chelating agents tested were 8-quinolinol (HOx), dithizone (HDz), 1-(2-pyridylazo)-2-naphthol (PAN) and their alkylated analogues, 5-octyloxymethyl-8-quinolinol (HO8Q), di(phexylphenyl)thiocarbazone (C6HDz), 7-pentadecyloxy-1-(2-pyridylazo)-2-naphthol (C15PAN) and a series of N-alkylcarbonyl-N-phenylhydroxylamines (CnPHA, n = 3, 6, 9, 12). The distribution coefficients between membrane solvent and water were determined to evaluate the hydrophobicity of the agents. The potential-pH profiles of the membranes containing hydrophobic chelating agents demonstrated the generation of potentiometric responses, while less hydrophobic agents gave no response. A possible model for the generation of membrane potential is proposed. The charge separation is attained by the permselective uptake of metal cations by the chelating agent anion at membrane/solution interface, where the high hydrophobicity of the agent enables the anionic or deprotonated form of the agents to remain at the membrane/solution interface.     

New bis-macrocyclic complexes with transition metal ions

Template condensation of benzidine, formaldehyde, ethylenediamine or 1,3-diaminopropane, metal salt and 1-phenyl-1,3-butanedione or 2,3-butanedione in a 1:4:2:2 molar ratio results in the formation of two new series of binuclear pentaaza macrocyclic complexes: dichloro[1,1-phenylbis(7-methyl-9-phenyl-1,3,6,10,13-pentaazacyclotetradeca-6,9-diene) metal(II)], [M₂LCl₄] (M = Co^II, Cu^II, Fe^III and Zn^II) and dichloro[1,1-phenylbis(8,9-dimethyl-1,3,7,10,14-pentaazacyclopentadeca-7,9-diene) metal(II)], [M₂LCl₄] (M = Ni^II, Co^II, Cu^II and Cd^II). Both series were characterized by i.r., ¹H-n.m.r., u.v.–vis. spectral studies, conductivity and magnetic susceptibility measurements.     

Interactions of silver halides with metal chelates and chelating agents

Summary Electrokinetic data of negatively charged silver iodide solsin statu nascendi were obtained as a function of varying concentrations of two chelate complexes, Co(phen) ₃ ³⁺ and Co(dipy) ₃ ³⁺ . The measurements were carried out with sols at two different pl values (2.72 and 3.15) and at two pH values (3.0 and 7.0). The results were interpreted in terms of the theory of the electrical double layer based on the Stern-Langmuir adsorption model.

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Zusammenfassung Die elektrokinetischen Daten für negativ geladene Silberjodid-Solein statu nascendi wurden in Abhängigkeit von verschiedenen Konzentrationen von Co(phen) ₃ ³⁺ and Co(dipy) ₃ ³⁺ Komplexen bestimmt. Die Messungen wurden mit Solen bei zwei verschiedenen pI-Werten (2.72 und 3.15) und bei pH 3.0 und 7.0 durchgeführt. Die Resultate konnten durch die Doppelschicht-Theorie, die auf der Stern-Langmuirsche Adsorption beruht, erklärt werden.

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Part I, see Ref. 3; Part 11, Ref. 5.

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With 3 figures and 2 tables     

The interaction of divalent tin compounds with transition metal carbonyls

The reaction of tin(II) halides, cyclopentadienyls, and β-diketonates with Co₂(CO)₈, Fe₂(CO)₉, and Group VI metal carbonyls is described.     

Thermodynamic studies on complexation of divalent transition metal ions with some zwitterionic buffers for biochemical and physiological research

The interaction between the zwitterionic buffers (3-[N-bis(2-hydroxyethyl)amino]-2-hydroxy propane sulfonic acid, N-(2-actamido)-2-aminoethane sulfonic acid, and 3-[(1,1-dimethyl-2-hydroxyethyl)amino]-2-hydroxy propane sulfonic acid) with some divalent transition metal ions (Cu^II, Ni^II, Co^II, Zn^II, and Mn^II) were studied at different temperatures (298.15 to 328.15) K at ionic strength I = 0.1 mol · dm⁻³ NaNO₃ and in the presence of 10%, 30%, and 50% (w/w) dioxene by using potentiometry. The thermodynamic stability constants were calculated as well as the free energy change for the 1:1 binary complexation. The protonation constants of the zwitterionic buffers were also determined potentiometrically under the above conditions.