Coordination properties of vic-isonitrosoimines in their copper (II) and palladium (II) complexes

Preparation and structural characterization of palladium (II) complexes of ligands III-V and copper (II) complexes of III are reported. The elemental analyses of the complexes show that the metal: ligand ratio is 1 : 2. The electrical conductance in acetone shows the non-electrolytic nature of the complexes. The diamagnetic character suggests a gross square-planar geometry for the palladium (II) complexes. Copper (II) complexes are paramagnetic with/~eff.~l'90 B.M. Spectral data suggest that in all the complexes the ligand coordinates to the metal (II) symmetrically through isonitroso-nitrogen and imine-nitrogen, forming a ¡ membered chelate ring. Amine-exchange reactions of the complexes are discussed and compared on the basis of their structures.

A Comparative Study of Electrochemical Kinetic Parameters by the Potential Step Method. Electrode Reactions of CyDTA and EDTA Complexes of Cu(II) at DME

By using the same current-time (I-t) curves, electrochemical kinetic parameters are determined by two methods, (a) using the ratio of current at a given potential to the diffusion-controlled limiting current and (b) curve fitting method, for the reduction of Cu(II)–CyDTA complex. The analysis by the method (a) shows that the rate determining step involves only one electron although the overall reduction of the complex involves two electrons suggesting thereby the stepwise reduction of the complex. The nature of I-t curves suggests the adsorption of intermediate species at the electrode surface. Under these circumstances more reliable kinetic parameters can be obtained by the method (a) compared to that of (b). Similar observations are found in the case of reduction of Cu(II)–EDTA complex.

Thermal decomposition of titanyl oxalates II : Kinetics of decomposition of barium titanyl oxalate

Kinetics of the thermal decomposition of barium titanyl oxalate have been studied. Decomposition of the anhydrous oxalate is complex and deceleratory throughout. Kinetics of decomposition of the intermediate carbonate Ba2Ti2O5CO3 is greatly influenced by the thermal effects during its formation. The sigmoidal (α, t) curves obey a power law equation followed by first order decay. Presence of carbon in the vacuum prepared carbonate has a strong deactivating effect. Decomposition of the carbonate is accompanied by growth in particle size of the product, barium titanate.

Structural studies of analgesics and their interactions. II. The crystal structure of a 1:1 complex between antipyrine and salicyclic acid (salipyrine)

The complex crystallizes in the space group P21/c with four formula units in a unit cell of dimensions a= 12.747, b= 7.416, c= 17.894 A and/3= 90.2 °. The structure has been solved by the symbolic addition procedure using three-dimensional photographic data and refined to an R value of 0.079 for 2019 observed reflexions. The pyramidal nature of the two hetero nitrogen atoms in the antipyrine molecule is inter:nediate between that observed in free antipyrine and in some of its metal complexes. The molecule is more polar than that in crystals of free antipyrine but less so compared with that in metal complexes. In the salicylic acid molecule, the hydroxyl group forms an internal hydrogen bond with one of the oxygen atoms in the carboxyl group. The association between the salicylic acid and the antipyrine molecules is achieved through an intermolecular hydrogen bond with the other carboxyl oxygen atom in the salicylic acid molecule as the proton donor and the carboxyl oxygen atom of the antipyrine molecule as the acceptor.

Mossbauer effect studies of the thermal decomposition of iron(II) oxalate in hydrogen

Mössbauer-effect and X-ray studies were carried out on the product samples of the thermogravimetric analysis (TGA) and of the isothermal decomposition of iron(II) oxalate in flowing H2. Two types of sample configurations were employed for isothermal studies between 280 to 420°C for various periods of heating. Low temperature Mossbauer measurements at liquid nitrogen temperature were carried out to examine the superparamagnetic (SPM) contributions. From the spectra of samples decomposed at 340°C, in vertical experiments, the percentage SPM and percentage ferromagnetic (FM) area of Fe3O4 were estimated and an average size (˜167Å) for Fe3O4 was derived. Mossbauer measurements (at high temperatures) were carried out on Fe3C formed in horizontal experiments, for two samples decomposed at ˜320°C for 1 hr and 2 hr. An estimate of SPM and FM Fe3C was obtained by calculating KV, the anisotropy energy for the Fe3C in these two samples and values of 5.07 × 10−16 and 7.02 × 10−16 erg/sec, respectively, were obtained.

Electron spin resonance study of copper(II) doped ferroelectric ammonium sulphate

Single crystal electron spin resonance studies of Cu2+ doped ferroelectric ammonium sulphate ((NH4)2SO4, Tc = 223 K) are reported at 300 and 77 K. The Cu2+ ion is found to enter the lattice interstitially with a trigonal bipyramidal coordination. Proton superhyperfine interaction is found for magnetic field directions close to the a-axis. Changes are observed in the 77 K recordings indicating a distortion of the trigonal bipyramid consistent with crystal structure data. An increase of the proton superhyperfine constant in the ferroelectric phase is indicative of stronger hydrogen bonding. The Cu2+ ion doped as an impurity in a trigonal bipyramid environment in a diamagnetic host lattice is reported for the first time.

Wrought aluminum-nickel alloys for high strength-high conductivity applications

Aluminum-Nickel alloys ranging from 0.06 pct to 6.1 pct (by wt) Ni have been developed for high strength-high conductivity applications. These alloys were produced by solidification in a permanent mold followed by homogenization, hot extrusion or hot rolling and cold drawing to wire form. This sequence of fabrication a) led to the production of fine fibrous dispersoids of NiAl3 as part of the Al-NiAl3 eutectic during the initial casting operation, b) permitted the retention of fine fibrous dispersiods of NiAl3 produced during casting without any significant coarsening during processing and c) led to uniform dispersion and general alignment of these fibrous dispersoids along a given direction in the product without any measurable fiber-matrix separation, extensive fiber-fragmentation or crack production in the matrix. These alloys can be processed to wire form as easily as aluminum and when processed by the above sequence, possess very attractive combination of high strength-high electrical conductivity. Tensile strengths range from 173 N/mm2 (at 0.6 pct Ni) to 241 N/mm2 (at 6.1 pct Ni) in combination with corresponding conductivity values between 62 pct IACS and 55.5 pct IACS. The wires also possess attractive yield strength; for instance, the 0.2 pct off-set strength of Al-6.1 pct Ni wire is 213 N/mm2. Using simple composite rules, the estimated strength and the conductivity of NiAl3 fibers were found to be 1380 N/mm2 and 18 pct IACS respectively, in these wires.

Vibration-rotation pattern in acetylene. II. Introduction of Coriolis coupling in the global model and analysis of emission spectra of hot acetylene around 3 mu m

A high temperature source has been developed and coupled to a high resolution Fourier transform spectrometer to record emission spectra of acetylene around 3 mu m up to 1455 K under Doppler limited resolution (0.015 cm(-1)). The nu(3)-ground state (GS) and nu(2)+nu(4)+nu(5)(Sigma(+)(u) and Delta(u))-GS bands and 76 related hot bands, counting e and f parities separately, are assigned using semiautomatic methods based on a global model to reproduce all related vibration-rotation states. Significantly higher J-values than previously reported are observed for 40 known substates while 37 new e or f vibrational substates, up to about 6000 cm(-1), are identified and characterized by vibration-rotation parameters. The 3 811 new or improved data resulting from the analysis are merged into the database presented by Robert et al. [Mol. Phys. 106, 2581 (2008)], now including 15 562 lines accessing vibrational states up to 8600 cm(-1). A global model, updated as compared to the one in the previous paper, allows all lines in the database to be simultaneously fitted, successfully. The updates are discussed taking into account, in particular, the systematic inclusion of Coriolis interaction.

X-ray studies of crystalline complexes involving amino acids. II. The crystal structure of L-arginine L-glutamate

Abstract is not available.

Interaction of palladium (II) with DNA

The nature of interaction of palladium(II) with calf thymus DNA was studied using viscometry, ultraviolet, visible and infrared spectrophotometry and optical rotatory disperison and circular dichroism measurements. The results indicate that Pd(II) interacts with both the phosphate and bases of DNA. The ORD/CD data indicate that the binding of Pd(II) to DNA brings about considerable conformational changes in DNA.

Preparation of Palladium(II) Complexes of Isonitrosoacetylacetoneimines Having O- and N-Coordinated Isonitroso Groups

Methods for the preparation of palladium(II) complexes of the type Pd(R-IAI)(IAI'), where IAI' is the anion of isonitrosoacetylacetoneimine and R-IAI, its N-alkyl or N-aryl derivative, are given.

Metal chelates in vinyl polymerization. II. Mechanism of initiation by Fe(DPM)3

The nature of the interaction between the unsaturated monomer and the chelate, Fe(DPM)3, is studied in detail. The interaction is found to occur only in solution. The stoichiometry of interaction and the equilibrium constant are evaluated. With the help of spectral evidence, attempts are made to point out the specific sites of interaction.

New ternary copper(II) complexes of L-alanine and heterocyclic bases: DNA binding and oxidative DNA cleavage activity

Four new ternary copper(II) complexes of alpha-amino acid having polypyridyl bases of general formulation [Cu(L-ala)(B)(H2O)](X)(1-4), where L-ala is L-alanine, B is an N,N-donor heterocyclic base, viz. 2,2'-bipyridine (bpy, 1), 1,10-phenanthroline (phen, 2) and 5,6-phenanthroline dione (dione, 3), dipyrido[3,2:2',3'-f] quinoxaline (dpq, 4), and X = ClO4-/NO3- are synthesized, characterized by various spectroscopic and X-ray crystallographic methods. The complexes show a distorted square-pyramidal (4 + 1) CuN3O2 coordination geometry. The one-electron paramagnetic complexes (1-4) display a low energy d-d band near 600 nm in aqueous medium and show a quasi-reversible cyclic voltammetric response due to one-electron Cu(II)/Cu(I) reduction near - 100 mV (versus SCE) in DMF-0.1 M TBAP. Binding interactions of the complexes with calf thymus DNA (CT-DNA) were investigated by UV-Vis absorption titration, ethidium bromide displacement assay, viscometric titration experiment and DNA melting studies. All the complexes barring the complexes 1 and 3 are avid binder to the CT-DNA in the DNA minor groove giving an order: 4 > 2 >>>1, 3. The complexes 2 and 4 show appreciable chemical nuclease activity in the presence of 3-mercaptopropionic acid (MPA) as a reducing agent. Hydroxyl radical was investigated to be the DNA cleavage active species. Control experiments in the presence of distamycin-A show primarily minor groove-binding propensity for the complexes 2 and 4 to the DNA.

X-ray crystal structure of a ternary copper(II) vitamin B6 complex, hydroxo(2,2'-bipyridyl)(pyridoxinato) copper(II) monohydrate. A rare example of monodentate coordination of copper(II) by the hydroxyl ion

A ternary metal complex involving Vitamin B6 with the formula [Cu(bipy)(pn) (OH)]H2O (bipy = 2,2'²-bipyridine, PN = anionic pyridoxine) has been synthesized and studied in the solid state by means of spectroscopy and X-ray crystallography. The geometry around copper(II) is distorted square pyramidal, two oxygens from phenolic and 4-(hydroxymethyl) groups of pn, two nitrogens from bipy and an axial OH- ion forming the coordination sphere. In this structure pn exists in a new anionic form with deprotonation of the phenolic group. The structure also provides a rare example of monodentate hydroxyl coordination to copper.