NIEDERKOORDINIERTE PHOSPHORVERBINDUNGEN, 701 1-METALLA-2,5-DIPHOSPHA PENTA-1,3-DIENE DURCH 1,4-ADDITION VON METALLCARBONYLCYCLOPENTADIENYLHYDRIDEN AN 1,4-DIPHOSPHABUTA-1,3-DIEN

Abstract

Reactions of carbonyl cyclopentadienyl hydrides from molybdenum and tungsten with 1,4-diphosphabuta-1,3-diene yield metalla-diphospha-pentadiene with a metal-phosphorus-double bond.

Metalla-diphosphapentadiene mit einer Metall-Phosphor-Doppelbindung werden durch Umsetzung von Carbonylcyclopentadienylhydriden des Molybdäns und Wolframs mit einem 1,4-Diphospha-buta-1,3-dien erhalten.     

On the redox reactions of radicals with AlIII(phthalocyaninate) pendants covalently bonded to poly(ethyleneamide). Mechanistic alterations when radicals are formed inside pockets of micelle‐like polymer aggregates

The mechanisms of the redox reactions between a polymer containing Al(III) sulfonated phthalocyanine pendants, (Al^III(^?NHS(O₂)trspc)^2?)₂, and radicals have been investigated in this work. Pulse radiolysis and photochemical methods were used for these studies. Oxidizing radicals, OH^?, HCO₃^?, (CH₃)₂COHCH₂^?, and N₃^?, as well as reducing radicals, e_aq^?, CO₂^??, and (CH₃)₂C^?OH, respectively accept or donate one electron forming pendent phthalocyanine radicals, Al^III(^?NHS(O₂)trspc ^?)^{? or 3?}. The kinetics of the redox processes is consistent with a mechanism where the pendants react with radicals formed inside aggregates of five to six polymer strands. Electron donating radicals, that is, CO₂^?? and (CH₃)₂C^?OH, produce one‐electron reduced phthalocyanine pendants that, even though they were stable under anaerobic conditions, donated charge to a Pt catalyst. While the polymer was regenerated in the Pt catalyzed processes, 2‐propanol and CO₂ were respectively reduced to propane and CO. The reaction of SO₃^?? radicals with the polymer stood in contrast with the reactions of the radicals mentioned above. A first step of the mechanism, the coordination of the SO₃^?? radical to the Al(III), was subsequently followed by the formation of a SO₃^?? ‐ phthalocyanine ligand adduct. The decay of the SO₃^?? ‐ phthalocyanine ligand adduct in a ～10² ms time domain regenerates the polymer, and it was attributed to the dimerization/disproportionation of SO₃^?? radicals escaping from the aggregates of polymer. © 2012 Wiley Periodicals, Inc. J Polym Sci Part A: Polym Chem, 2012     

Effect of solvent on the construction of Co(II) coordination polymers containing a semi-rigid bis(benzimidazole) derivative: syntheses,structures, and properties

Two Co(II) coordination polymers, [CoL(npa)]·2H₂O (1) and [CoL(Hnpa)₂] (2) (L = 1,4-bis(5,6-dimethylbenzimidazole-1-yl)benzene, H₂npa = 5-nitroisophthalic acid), have been synthesized in different solvent systems and characterized by Infrared (IR) spectroscopy, elemental analysis, and powder and single crystal X-ray diffraction. Compound 1 was synthesized under solvothermal conditions with DMF as solvent and had a pair of L ligands adopting a μ₂-bridging mode and connecting two Co²⁺ cations to generate a 26-membered Co₂L₂ loop. The npa^2? link adjacent Co₂L₂ loops via a bis(monodentate) bridging mode to create a 1-D channel-like chain structure. Compound 2 was obtained under hydrothermal conditions, and the carboxylate of the monodeprotonated Hnpa^? adopt a μ₁-η^0?:?η¹ coordination to connect adjacent Co²⁺ cations into a 2-D polymeric layer. The μ₂-bridging L ligands connect adjacent 2-D [Co(Hnpa)]_n polymeric layers into a 3-D NaCl-like framework. The Co²⁺ cations and the L ligands in compounds 1 and 2 exhibit different coordination geometries and conformations. Effects of solvents on the construction of Co(II) coordination polymers were investigated. In addition, the electrochemical behavior of carbon paste electrodes containing 1 and 2 and the thermal stabilities of 1 and 2 were investigated.     

SPECTROPHOTOMETRIC STUDY OF COMPLEX FORMATION BETWEEN SOME ALKALI AND ALKALINE EARTH CATIONS AND SEVERAL CONVENTIONAL (N,N), (N,O) AND (O,O) LIGANDS IN 95% ETHANOL

Abstract

The complexation of Li⁺, Na⁺, Mg²⁺ and Ca²⁺ with 1,10-phenanthroline, 2,2′-bipyridine, 1,2-phenylenediamine, 2-aminopyridine, 8-hydroxyquinoline, catechol and ethylene glycol was studied in 95% ethanol by means of a competitive spectrophotometric method using murexide as indicator. Formation constants of 1:1 conplexes were determined. In the case of all ligands used, the stability of the complexes was found to vary in the order Mg²⁺ > Ca²⁺ > Li⁺ > Na⁺. It was found that the structure influences the formation and stability of resulting complexes. Effects of various parameters on complexation are discussed.     

A new stable porous Pr-organic framework constructed by multi-iodine-substituted aromatic polycarboxylates: Synthesis,characterization, and selective adsorption of dyes

abstract

Poly[tris(dimethylformamide)(μ3-2,4,6-triiodol-1,3,5-benzene tricarboxylic acid)-praseodymium (III)] {Pr(TIBTC)(DMF)₃}_n (1) (H₃TIBTC = 2,4,6-triiodo-1,3,5-benzene tricarboxylic acid) was synthesized by the reaction of Pr(NO₃)₃·6H₂O and H₃TIBTC at 85°C in a pyrex vial. 1 was characterized by elemental analysis, IR, UV–vis, TGA, PXRD, and atomic force microscopy analytical means. Each of the central Pr ions and the three carboxyl groups from the same ligand constitute a SBU, which is then joined by a carboxyl group to form a building block. In order to further explore the functional properties of 1, we used this compound for adsorption experiments. It is found that 1 can effectively adsorb anionic dyes in aqueous solutions. In particular, there is a good adsorption efficiency for coomassie brilliant blue R-250. Therefore, 1 shows good prospects for selective adsorption of anionic dyes from wastewater solution.     

Two photoluminescent pentanuclear homo- and hetero-metal complexes based on benzotriazole bridge

Two new discrete Btz-bridged pentanuclear metal complexes, [HDMF][NaHg₄(Btz)₆I₄] (1) and [Zn₅(Btz)₆(L)₃(Ac)]?·?0.5MeOH?·?0.5H₂O (2) (Btz?=?deprotonated benzotriazole, L?=?p-aminobenzoate, HDMF?=?protonated DMF, and Ac?=?acetate), were synthesized using three-layered diffusion and natural evaporation methods, respectively. In 1, the pentanuclear anion [NaHg₄(Btz)₆I₄]^? is composed of a tetrahedral arrangement of four four-coordinate Hg(II) ions centered on the six-coordinate Na(I), and thereby forming a rare Btz-bridged hetero-metal complex. Compound 2 is a neutral pentanuclear homo-metal complex, consisting of a tetrahedral arrangement of four five-coordinate Zn(II) ions centered on the fifth six-coordinate Zn(II). The thermal stabilities and solid-state photoluminescence of the two complexes have been investigated.     

Preface

Abstract

The FT-IR and Raman spectra of eight new complexes of formula ML₂Ni(CN)₄ (where M = Mn, Fe, Co, Ni, Cu or Cd and L = 2-chloropyridine; M = Ni or Cd and L = 2-bromopyridine) are reported. The spectroscopic results indicate that the complexes have structures consisting of corrugated polymeric layers of [M-Ni(CN)₄]∞ with 2-substituted pyridine molecules bound directly to the metal (M). For a given ligand (2-Clpy or 2-Brpy) the effects of metal-ligand bond formation on the ligand modes are examined. Metal-ligand bond strengths of the halo-derivatives of pyridine (L = 2-Clpy or 2-Brpy), inferred by the effects on frequency shifts of certain ligand modes, have also been compared.     

Ligational behavior of new mononucleating NOO ethyl pyruvate Schiff base towards 3d metal(II) ions: an emphasis on antiproliferative and photocleavage property

A series of Co(II), Ni(II), Cu(II), and Zn(II) complexes of a tridentate hydrazone were prepared and characterized by various spectro‐analytical techniques and magnetic moment studies. The complexes were found to be monomeric and non‐electrolytes. The copper complex is electrochemically active in the applied potential range. The compounds synthesized in the present study have shown promising antiproliferative activity when screened using the in vitro method against two human cancer cell lines: HeLa and HepG2. The Escherichia coli DNA‐binding properties of all the compounds were investigated with UV–visible absorption spectrophotometric titrations, viscosity measurements, DNA melting experiments and gel electrophoreses measurements. The compounds were demonstrated to act as DNA intercalators with appreciable DNA‐binding constant values. Copyright © 2012 John Wiley & Sons, Ltd.     

A vectorial algorithm with finite element method for prediction of powder segregation in metal injection molding

The design of the mold and the choice of the injection parameters for metal injection molding (MIM) is required to maintain homogeneity of the filled mixture. However, powder segregation is unavoidable in MIM because of the significant difference in densities of the metallic powder and the polymer binder. To achieve an effective prediction of segregation effect, a biphasic model based on mixture theory is employed. The viscous behaviors of each phase and the interaction coefficient between the flows of the two phases should be determined. The solution of two coupled Navier–Stokes equations results in a tremendous computation effort. The previous development of an explicit algorithm makes the biphasic simulation much faster than that of the classic methods. However, it is strongly desired to reduce or even eliminate the numerous global solutions for pressure fields at each time step. Hence, a new vectorial algorithm is proposed and developed to perform the simulation only by vectorial operations. It provides the anticipated efficiency in the simulation of biphasic modeling, and the advantage to use the classic elements of equal‐order interpolations. Some results produced by the two algorithms are compared with the experimental values to validate the new vectorial algorithm. Copyright © 2012 John Wiley & Sons, Ltd.     

Fluorescence of metal complexes of 8-hydroxyquinoline derivatives in aqueous micellar media

The fluorescence characteristics of 8-hydroxyquinoline derivative complexes of A1(III), Ga(III), In(III), Zn(II), and Be(II) in differently charged micellar media are reported. For most of the chelates studied, large increases are observed in micellar media compared with those obtained in hydroorganic solvents. However, some exceptions are observed, of which the low fluorescence of Zn(II) chelates in anionic sodium lauryl sulfate media is the most noticeable.