Organometallic chemistry of diphosphazanes. Part 7. Platinum(II), palladium-(o), -(I) and -(II) complexes of RN[P(OPh)2]2(R = Me or Ph)

The reactions of [MCl2(cod)](M = Pd or Pt, cod = cycloocta-1,5-diene) with RN[P(OPh)2]2[R = Me (L1) or Ph (L2)] afford the chelate complexes [MCl2L1] and [MCl2L2]. The dinuclear palladium(O) complex, [Pd2L13] has been synthesized by starting from [Pd2(dba)3](dba = dibenzylideneacetone). Redox condensation of [Pd2(dba)3] and [PdCl2(PhCN)2] in the presence of the diphosphazane ligands gives the dinuclear palladium(I) complexes [Pd2Cl2L12] and [Pd2Cl2L22]. The structures of the complexes have been deduced from 1H and 31P NMR spectroscopic data. Single-crystal X-ray diffraction studies confirm the structures of [Pd2L13] and [Pd2Cl2L22].

Palladium(II) chloride complexes of bis(pyrazolyl)cyclotriphosphazenes

Reactions of the bis(3,5-dimethylpyrazolyl)cyclotriphosphazene derivatives gem-N3P3(MeNCH(2)CH(2)O)(2)(dmp)(2) (1) and nongeminal cis-N3P3(OPh)(4)(dmp)(2) (2) with PdCl2 afford complexes of the type [PdCl2.(L)] (L = 1 or 2). In these complexes, the phosphazenes act as bidentate NN-donor ligands with the two pyrazolyl pyridinic nitrogen atoms bonded to the metal, thus forming a six- and an eight-membered chelate ring, respectively. The structures of 2 and [PdCl2.(2)] (4) have been confirmed by single-crystal X-ray diffraction. Crystal data for 2: a = 16.759(2) Angstrom, b = 10.788(3) Angstrom, c = 19.635(9) Angstrom, beta = 101.61(3)degrees, P2(1/c), Z = 4, R = 0.038 for 4688 reflections with F > 5 sigma(F). Crystal data for 4: a = 9.701(3) Angstrom, b = 24.853(4) Angstrom, c = 15.794(4) Angstrom, beta = 101.46(2)degrees, P2(1/n), Z = 4, R = 0.030 for 5416 reflections with F > 5 sigma(F).

Processing maps for hot working of Cu-Ni-Zn alloys. Part I - Alpha-nickel silver

The constitutive behaviour of agr — nickel silver in the temperature range 700–950 °C and strain rate range 0.001–100 s–1 was characterized with the help of a processing map generated on the basis of the principles of the ldquodynamic materials modelrdquo of Prasadet al Using the flow stress data, processing maps showing the variation of the efficiency of power dissipation (given by 2m/(m+1) wherem is the strain-rate sensitivity) with temperature and strain rate were obtained, agr-nickel silver exhibits a single domain at temperatures greater than 750 °C and at strain rates lower than 1s–1, with a maximum efficiency of 38% occurring at about 950 °C and at a strain rate of 0.1 s–1. In the domain the material undergoes dynamic recrystallization (DRX). On the basis of a model, it is shown that the DRX is controlled by the rate of interface formation (nucleation) which depends on the diffusion-controlled process of thermal recovery by climb. At high strain rates (10 and 100s–1) the material undergoes microstructural instabilities, the manifestations of which are in the form of adiabatic shear bands and strain markings.

Reaction of spironaphthalenones with hydroxylamine: Part II. Structure of product in the reaction of 1′-substituted spironaphthalenone.

Reaction of 1′-aryl substituted spironaphthalenones 1a–d with hydroxylamine hydrochloride in ethanol gave substituted cinnamic ester derivatives 4a–d. Similarly, reaction of spironaphthalenone 1a with different alcohols gave the corresponding esters 4i–m. Reaction of unsymmetrical spironaphthalenones 1e–h with hydroxylamine hydrochloride in presence of ethanol gave the respective esters 4e–h. All the esters were characterised by their spectral data.

Solvation and axial ligation properties of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)

he solvation of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)[Zn(obtpp)], in twelve different solvents results in large red shifts of the B and Q bands of the porphyrin accompanied by enhanced absorbance ratios of the Q bands. These observations are ascribed to the destabilisation of the highest occupied molecular orbital a2u of the porphyrin arising from a flow of charge from the axial ligand to the porphyrin ring through the zinc(II) ion. The binding constants of adducts of [Zn(obtpp)] with neutral bases have been found to be an order of magnitude greater than those observed for the corresponding adducts of (5,10,15,20-tetraphenylporphyrinato)-zinc and vary in the order piperidine > imidazole > pyridine > 3-methylpyridine > pyridine-3-carbaldehyde. The enhanced binding constants and large spectral shifts are interpreted in terms of the electrophilicity of [Zn(obtpp)] induced by the electron-withdrawing bromine substituents in the porphyrin core. The structure of [Zn(obtpp)(PrCN)2] has been determined; it reveals six-co-ordinated zinc(II) with two long Zn–N distance [2.51(4), 2.59(3)Å]. The porphyrin is non-planar and displays a saddle-shaped conformation.

Stabilization of α-nickel hydoxide in the presence of organic additives: chemical route to bulk synthesis

Organic molecules such as glucose or lactose mediate the synthesis and stabilize alpha-nickel hydroxide in a simple precipitation reaction, while, in the absence of these additives, beta-nickel hydroxide is formed. The additives are not incorporated in the product phase.

Stereochemical properties and x-ray structure of a water-soluble diastereomeric (arene)ruthenium(II) Schiff-base complex: [Ru(.eta.-MeC6H4Pri-p)(H2O)(L*)](ClO4), containing a weakly bound aqua ligand [HL* = (S)-(.alpha.-methylbenzyl)salicylaldimine]

An air-stable and water-soluble diastereomeric half-sandwich ruthenium(I1) complex, [Ru(s-MeCsH4Pr'-p)(H*O)-(L*)] (C104) (l), has been isolated and structurally characterized [HL* = (27)-(a methylbenzyl)salicylaldimine,2-HOC6H4CH-NCHMePhI. Complex 1, Czd-I3oNO&lRu, crystallizes in the noncentric triclinic space group P1 with a = 9.885(1) A, b = 10.185(1) A, c = 14.187(2) A, a = 110.32(1)', 6 = 102.17(1)', y = 102.41(1)O, V=1243( 1) A3, and 2 = 2. The X-ray structure shows the presence of two diastereomers in a 1:l ratio having RR,,,SCand SR,,,&c onfigurations. The Ru-OHz bond distances are considerably long, and the values for RR, - a~n d SRu-1isomers are 2.1 19(5) and 2.203(5) A, respectively. The aqua complex (1) exists as a single diastereomer in solution,and it forms stable adducts with P-, N-, and halide-donor ligands. The stereochemical changes associated with adduct-forming reactions follow an inversion order: PPhs >> P(OMe)3 > pyridine bases >> halides (I, Br, Cl) >H20.

Cobalt(II) complexes of terpyridine bases as photochemotherapeutic agents showing cellular uptake and photocytotoxicity in visible light

Cobalt(II) complexes of terpyridine bases Co(L)(2)](ClO4)(2) (1-3), where L is 4'-phenyl-2,2':6',2''-terpyridine (ph-tpy in 1), 4'-(9-anthracenyl)-2,2':6',2''-terpyridine (an-tpy in 2) and 4'-(1-pyrenyl)-2,2':6',2''-terpyridine (py-tpy in 3), are prepared and their photo-induced DNA and protein cleavage activity and photocytotoxic property in HeLa cells studied. The 1 : 2 electrolytic and three-electron paramagnetic complexes show a visible band near 550 nm in DMF-Tris-HCl buffer. The complexes 1-3 show emission spectral bands at 355, 421 and 454 nm, respectively, when excited at 287, 368 and 335 nm. The quantum yield values for 1-3 in DMF-H2O (2 : 1 v/v) are 0.025, 0.060 and 0.28, respectively. The complexes are redox active in DMF-0.1 M TBAP. The Co(III)-Co(II) and Co(II)-Co(I) couples appear as quasi-reversible cyclic voltammetric responses near 0.2 and -0.7 V vs. SCE, respectively. Complexes 2 and 3 are avid binders to calf thymus DNA giving K-b value of similar to 10(6) M-1. The complexes show chemical nuclease activity. Complexes 2 and 3 exhibit oxidative cleavage of pUC19 DNA in UV-A and visible light. The DNA photocleavage reaction of 3 at 365 nm shows formation of singlet oxygen and hydroxyl radical species, while only hydroxyl radical formation is evidenced in visible light. Complexes 2 and 3 show non-specific photo-induced bovine serum albumin protein cleavage activity at 365 nm. The an-tpy and py-tpy complexes exhibit significant photocytotoxicity in HeLa cervical cancer cells on exposure to visible light giving IC50 values of 24.2 and 7.6 mu M, respectively. Live cell imaging study shows accumulation of the complexes in the cytosol of HeLa cancer cells.

Temperature dependence of hydrogen evolution reaction on nickel oxide electrode in sealed nickel/cadmium cells

The impedance of sealed nickel/cadmium cells around a cell e.m.f. of 0.0 V was measured at five different temperatures between � 10 and +30 °C. The results show that the behaviour is similar at all temperatures. Based on the experimental results, the relation between charge-transfer resistance (Rct) and temperature (T) has been established for the Volmer reaction. Further, the value of cathodic transfer coefficient (?) has been estimated.

Texture evolution and operative mechanisms during large-strain deformation of nanocrystalline nickel

The large-strain deformation of nanocrystalline nickel was investigated at room temperature and cryogenic (liquid N-2) temperature. Deformation mechanisms ranging from grain boundary sliding to slip, operate due to a wide distribution of grain sizes. These mechanisms leave their finger print in the deformation texture evolution during rolling of nanocrystalline nickel. The occurrence and severance of different mechanisms is understood by a thorough characterization of the deformed samples using X-ray diffraction, X-ray texture measurements, electron back-scattered diffraction and transmission electron microscopy. Crystal plasticity-based viscoplastic self-consistent simulations were used to further substantiate the experimental observations. Thus, a comprehensive understanding of deformation behavior of nanocrystalline nickel, which is characterized by simultaneous operation of dislocation-dominated and grain boundary-mediated mechanisms, has been developed.

The Determination of the Surface Tensions of Liquid-Iron, Nickel and Iron-Nickel Alloys using the electromagnetic Oscillating Droplet Technique

An oscillating droplet method combined with electromagnetic levitation has been applied to determine the surface tensions of liquid pure iron, nickel and iron-nickel alloys as a function of the temperature. The natural frequency of the oscillating droplet is evaluated using a Fourier analyser. The theoretical background of this method and the experimental set-up were described, and the influence of magnetic field strength was also discussed. The experimental results were compared with those of other investigators and interpreted using theoretical models (Butler's equation, subregular and perfect solution model for the surface phase).

The Determination of the Surface Tensions of Nickel Sulfur Alloys using the Electromagnetic Oscillating Droplet Technique

An oscillating droplet method combined with electromagnetic levitation technique has been applied to determine the surface tensions of liquid nickel sulphur alloys as a function of the temperature and composition. The natural frequency of the oscillating droplet is evaluated using a Fourier analyser, and the influence of magnetic field strength on the surface tension was considered. Furthermore, the applicability of Butler's equation and subregular solution model for the surface was shown to predict the surface tension of the systems containing the surface active elements.

Time-domain-finite-wave analysis of the engine exhaust system by means of the stationary-frame method of characteristics. Part II. Computed results and experimental corroboration thereof

Time-domain-finite-wave analysis of engine exhaust systems is usually carried out by means of the method of characteristics. The theory and the computational details of the stationary-frame method have been worked out in the accompanying paper (part I). In this paper (part II), typical computed results are given and discussed. A setup designed for experimental corroboration is described. The results obtained from the simulation are found to be in good agreement with experimental observations.

On the exothermic peak during annealing of electrodeposited nanocrystalline nickel

Nanocrystalline metals frequently exhibit poor thermal stability, and the exothermic peak in differential scanning calorimetry is usually attributed to grain growth. We show from experiments on electrodeposited nano-Ni with varying levels of S, and tests with microcrystalline Ni and S powders, that the exothermic peak is associated with the formation of a nickel sulfide phase and concurrent grain growth. Analysis suggests that segregation plays a more important role in limiting grain growth than second-phase particles in nano-Ni. (C) 2010 Acta Materialia Inc. Published by Elsevier Ltd. All rights reserved.