The synthesis and catalytic activity of poly(bis(imino)pyridyl) iron(II) metallodendrimer

The first and second generation carbosilane dendrimers with silicon hydride terminated were synthesized, and then reacted with bis(imino)pyridyl containing allyl [4-CH2==CHCH2-2,6-(Pr2C6H3N)-Pr-i==CMe(C5H3N)MeC==N(2,6-'Pr2C6H3)], in the presence of H2PtCl6 as a hydrosilylation catalyst, to afford the first and second generation carbosilane supported ligands. Complexation reactions with FeCl(2)(.)4H(2)O give rise to iron-containing carbosilane dendrimers with FeCl2 moieties bound on the periphery. The metallodendrimers were used as catalyst precursors, activated with modified methylaluminoxane, for the polymerization of ethylene. In the case of low Al/Fe molar ratio, the metallodendrimers display much higher catalytic activity towards ethylene polymerization and produce much higher molecule weight polyethylenes than the corresponding single-nuclear complex under the same conditions.

Effect of La/Ce ratio on the structure and electrochemical characteristics of La0.7-xCexMg0.3Ni2.8Co0.5 (x=0. 1-0.5) hydrogen storage alloys

The effect of La/Ce ratio on the structure and electrochemical characteristics of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1, 0.2, 0.3, 0.4, 0.5) alloys has been studied systematically. The result of the Rietveld analyses shows that, except for small amount of impurity phases including LaNi and LaNi2, all these alloys mainly consist of two phases: the La(La, Mg)(2)Ni-9 phase with the rhombohedral PuNi3-type structure and the LaNi5 phase with the hexagonal CaCU5-type structure. The abundance of the La(La, Mg)(2)Ni-9 phase decreases with increasing cerium content whereas the LaNi5 phase increases with increasing Ce content, moreover, both the a and cell volumes of the two phases decrease with the increase of Ce content. The maximum discharge capacity decreases from 367.5 mAh g(-1) (x = 0.1) to 68.3 mAh g(-1) (x = 0.5) but the cycling life gradually improve. As the discharge current density is 1200 mA g(-1), the HRD increases from 55.4% (x = 0.1) to 67.5% (x = 0.3) and then decreases to 52.1% (x = 0.5). The cell volume reduction with increasing x is detrimental to hydrogen diffusion D and accordingly decreases the low temperature dischargeability of the La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1-0.5) alloy electrodes.

Bronsted guanidine acid-base ionic liquids: Novel reaction media for the palladium-catalyzed Heck reaction

Bronsted acid-base ionic liquids (GILs) based on guanidine and acetic acid are efficient reaction media for palladium-catalyzed Heck reactions. They offer the advantages of high activity and reusability. GIL2 plays multiple roles in the reaction: it could act as solvent, as a strong base to facilitate beta-hydride elimination, and as a ligand to stabilize activated Pd species.

Crystallographic and electrochemical characteristics of icosahedral quasicrysyalline Ti45-xZr35-xNi17+2xCu3 (x=0-8) powders

Ti45--xZr35--xNi17+2rCU3 (x=0, 2, 4, 6 and 8) icosahedral quasicrystalline phase (I-phase) alloy powders are synthesized by mechanical alloying and subsequent annealing techniques, and the crystallographic and electrochemical characteristics are investigated. The alloy powders are I-phase, and the quasi-lattice constant decreases with increasing x value. The maximum discharge capacity of the I-phase alloy electrodes first increases and then decreases with increasing x value, and the Ti39Zr26Ni29Cu3 I-phase electrode exhibits the highest discharge capacity of 274 mAh g(--1). The high-rate dischargeability at the discharge current density of 240mA g(--1) increases from 55.31 % (x= 0) to 74.24% (x= 8). Cycling stability also increases with increasing x value. The improvement in electrochemical characteristics may be ascribed to the added nickel, which not only improves the electrochemical activity, but also makes the alloy more resistant to oxidation.

Electrochemical properties of amorphous and icosahedral quasicrystalline Ti45Zr35Ni17Cu3 powders

Ti45Zr35Ni17Cu3 amorphous and single icosahedral quasicrystalline powders were synthesized by mechanical alloying and subsequent annealing at 855 K. Microstructure and electrochemical properties of two alloy electrodes were characterized. When the temperature was enhanced from 303 to 343 K, the maximum discharge capacities increased from 86 to 329 mAh g(-1) and 76 to 312 mAh g(-1) for the amorphous and quasicrystalline alloy electrodes, respectively. Discharge capacities of two electrodes decrease distinctly with increasing cycle number. The I-phase is stable during charge/discharge cycles, and the main factors for its discharge capacity loss are the increase of the charge-transfer resistance and the pulverization of alloy particles. Besides the factors mentioned above, the formation of TiH2 and ZrH2 hydrides is another primary reason for the discharge capacity loss of the amorphous alloy electrode.

Crystallographic and electrochemical characteristics of La0.7Mg0.3Ni3.5-x (Al0.5Mo0.5)(x) (x=0-0.8) hydrogen storage alloys

The crystal structure, hydrogen storage property and electrochemical characteristics of the La0.7Mg0.3Ni3.5-x(Al0.5Mo0.5), (x=0-0.8) alloys have been investigated systematically. It can be found that with X-ray powder diffraction and Rietveld analysis the alloys are of multiphase alloy and consisted of impurity LaNi phase and two main crystallographic phases, namely the La(La, Mg)(2)Ni-9 phase and the LaNi5 phase, and the lattice parameter and the cell volume of both the La(La, Mg)(2)Ni-9 phase and the LaNi5 phase increases with increasing A] and Mo content in the alloys. The P-C isotherms curves indicate that the hydrogen storage capacity of the alloy first increases and then decreases with increasing x, and the equilibrium pressure decreases with increasing x. The electrochemical measurements show that the maximum discharge capacity first increases from 354.2 (v = 0) to 397.6 mAh g(-1) (x = 0.6) and then decreases to 370.4 mAh g(-1) (x= 0.8). The high-rate dischargeability of the alloy electrode increases lineally from 55.7% (x=0) to 73.8% (x=0.8) at the discharge current density of 1200 mA g(-1). Moreover, the exchange current density of the alloy electrodes also increases monotonously with increasing x.

Kinetic and electrochemical properties of icosahedral quasicrystalline Ti45Zr35Ni17Cu3 powder

Kinetic and electrochemical properties of icosahedral quasicrystalline Ti45Zr35Ni17Cu3 alloy powder as negative electrode material of Ni-MH battery have been investigated at different temperatures. The calculated results show that the apparent activation enthalpy of the charge-transfer reaction is 43.89 kJ mol(-1), and the activation energy of hydrogen diffusion is 21.03 kJ mol(-1). The exchange current density and the diffusion coefficient of hydrogen in the bulky electrode increase with increasing temperature, indicating that increasing temperature is beneficial to charge-transfer reaction and hydrogen diffusion. As a result, the maximum discharge capacity, activation property and high-rate dischargeability are greatly improved with increasing temperature. However, the charge retention and the cycling stability degrade with the increase of the temperature.

Electrochemical characteristics and microstructure of Zr0.9Ti0.1Ni1.1Mn0.6V0.3-LaNi5 composite hydrogen storage alloys

AB(2-x)%LaNi5 (x =0, 1, 5, 10) composite alloys were prepared by melting Zr0.9Ti0.1Ni1.1Mn0.6V0.3 with a small amount of LaNi5 alloy as addition. The microstructure and electrochemical characteristics of the composite alloys were investigated by means of XRD, SEM, EDS and electrochemical measurements. It was shown that LaNi5 addition does not change the basic hexagonal C14 Laves phase of AB(2) alloys, but some second phases have segregated. It was found that the addition of LaNi5 greatly improves the activation property, high-rate dischargeability (HRD) and charge-discharge cycling stability of AB(2) Laves phase alloy. At current density of 1200 mA/g, HRD of the alloy increases from 38.92% (x =0) to 60.09% (x = 10). The capacity retention of the alloy after 200 charge-discharge cycles increases from 57. 10% (x = 0) to 83.86% (x = 5) and 67.31% (x = 10). The improvement of the electrochemical characteristics caused by LaNi5 addition seems to be related to formation of the second phases.

Crystallographic and electrochemical properties of ball-milled quasicrystalline Ti45Zr35Ni17Cu3 alloy with 20 mass% Ni

Icosahedral quasicrystalline Ti45Zr35Ni17Cu3 alloy powder was ball-milled with 20 mass% Ni, and the effect of the ball-milling time (t) on crystallographic and electrochemical characteristics were investigated. The amounts of icosahedral quasicrystalline and Ni phases decreased when ball-milling time increased from 30 to 180 min. The powder consisted of amorphous and (Ni and Ti) phases after 360 min of ball-milling. The maximum discharge capacity of the powder electrodes first increased from 89 (t = 0 min) to 192 mAh g(-1) (t = 180 min), and then decreased to 138 mAh g(-1) (t = 360 min). The high-rate dischargeability and the discharge capacity after 15 cycles increased with increasing ball-milling time.

Structures and electrochemical characteristics of several kinds of alloys

The structures and the electrochemical characteristics of La0.7-xCexMg0.3Ni2.8Co0.5 (x = 0.1-0.5) alloy, Ti0.25-xZrxV0.35Cr0.1Ni0.3 (x = 0.05-0.15) alloy and AB(3

Syntheses and crystal structures of mononuclear rhodium hydrido complexes from the reactions of [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 with various nitrogen ligands

Reactions of the Rh hydrido complex [Rh(H)(2)(PPh3)(2)(EtOH)(2)]ClO4 (1) With nitrogen ligands such as 2-(4-thiazolyl)benzimidazole (tbz). pyridazine (pdz), imidazole (im) and pyrimidine (pmd) in CH,Cl, afforded Various mononuclear Rh hydrido complexes, [Rh(H)(2)(PPh3)(2)(tbz)]CIO4 (2), [Rh(H)(2)(PPh3)(2)(pdZ)(2)]ClO(4)(.)2CH(2)Cl(2) (3). [Rh(H)Cl(PPh3)(2)(pdz)(2)](ClO4CH2Cl2)-C-. (4). [Rh(H)(2)(PPh3)(2)(im)(2)]ClO(4)(.)2CH(2)Cl(2) (5). [Rh(H)Cl(PPh3)(2)(im)(2)](ClO4CH2Cl2)-C-. (6). [Rh(H)(2)(PPh3)(2)(pmd)(2)](ClO4CH2Cl2)-C-. (7) and the Rh non-hydrido complex [RhCl2(pmd)(4)]ClO4 (8). The Rh complexes 2. 3, 5 and 6 were crystallographically characterized. The formation process was monitored by H-1 NMR and UV-Vis spectra. In all the Rh hydrido complexes, the Rh atom is coordinated by two PPh3. ligands in trans-positions and two nitrogen ligands in the cis-positions. The remaining sites Lire occupied by one or two hydride atoms to form a saturated 18-electron framework in a slightly distorted octahedral geometry. For complex 2 an appreciable inter-molecular pi interaction is observed between planes of tbz and PPh3 ligands, while an intra-molecular hydrogen bonding interaction between C-H and Cl atoms is found in complex 6.

Electrochemical characteristic of LaNi-based hydrogen storage alloys

Effect of purity of alloy components on the electrode performance of LaNi2 alloys was investigated. The results showed the purity of components had less effect on discharge capacity and self-discharge of LaNi2 alloys. Partial substitution of Al or Mn for Ni greatly improved discharge properties of LaNi2-xAlx, or LaNi2-yMny alloys as negative electrodes in MFl-Ni battery, 0.15less than or equal toxless than or equal to0.25; 0.15less than or equal toyless than or equal to0.25. In addition, surface treatment of LaNi1.8Al0.2 alloy electrode was performed by polymerizing cis-butenedioate with Co-60- gamma -ray radiation, which. had better affect on self-discharge and cycle life of the alloy electrodes at low temperature(-28 C-degrees).

Separation and determination of organogermanium compounds by ion chromatography

For nearly three decades, organogermanium compounds have become increasingly of interest owing to their extensive physiological and pharmaceutical activity. In this paper, two new high performance ion chromatographic methods for separation and determination of three kinds of organogermanium compounds beta-carboxyethylgermanium sesquioxide (I), beta-(alpha-methyl)-carboxyethylgermanium sesquioxide (II) and d-(beta-carboxyethyl)germanium hydroxide (III) were proposed. A Dionex DX-300 ion chromatograph equipped with a Dionex FED-II pulsed electrochemical detector (conductivity mode), and a Dionex AI-450 chromatography workstation was employed. The separation was achieved by using ion-exchange or ion-exclusion mechanism. The detection limits(S/N=3, expressed as germanium) for the three compounds were all below sub- mu g/mL level. The methods have been applied to the analysis of tonic oral drinks, and the average recoveries for the three compounds range from 95 - 108%. The results obtained were in agreement with those of hydride generation atomic fluorescence spectrometry (HG-AFS).

Synthesis and chemical properties of [Z]-1-[2-(triaryl stannyl)vinyl]cyclooctanol

The compounds of [Z]-1-[2-(triphenyl stannyl) vinyl] cyclooctanol (1) and [Z]-1-[2-(tri-p-tolyl stannyl) vinyl] cyclooctanol (2) were synthesized by the reactions of triphenyltin hydride and tri-p-tolyltin hydride with 1-ethynyl cyclooctanol. The crystal structure of compound 1 was determined. The reactions of compound 1 and 2 with IC1, Br-2, I-2 formed nine organotin halides. The organotin oxide or hydroxide were prepared by the reactions of [Z]-1-[2-(phenyl dibromo stannyl) vinyl] cyclooctanol (6) and [Z]-1-[2-(diphenyl monobromo stannyl) vinyl] cyclooctanol (5) with KOH. Three complexes were obtained by the reactions of [Z]-1-[2-(phenyl diiodide stannyl) vinyl] cyclooctanol (8) with three ligands (2,2'-bipyridyl,5-nitro-1,10-phenanthroline,8-Hydroxyquinoline). The sixteen new compounds synthesized in this paper were characterized by means of elemental analysis, IR, H-1 NMR. The reaction mechanism of triphenyltin hydride and tri-p-tolyltin hydride with 1-ethynyl cyclooctanol were also proposed.

Reactions of C-60 with R(3)SnH: A new synthetic route to C-60(RH)(n) and the property of C-60 to catalyze radical reactions

A new method for the preparation of polyalkyl and polyarenefullerene derivatives C-60(RH)(n)(R=Bu,n=1-3; R=Ph,n=1-10) by the reaction of C-60 with organotin hydride in toluene is described. Another series of products of stannanes R(a)Sn(b)H(c) (R=Bu, a=3-8, b=1-4, c=0-3 R=Ph, a=3-11, b=1-5, c=0-4) were also obtained, which shows that C-60 can catalyze polymerization of organic-tin. These products were determined by mass and infrared spectrometry. And the possible reaction mechanisms are discussed.