Electron microscope observation of lattice defects in the FeCr σ-phase

The lattice image of the FeCr σ-phase was observed by high-resolution electron microscopy with the c axis of the tetragonal cell parallel to the incident beam. It was found that bright dots of the observed image correspond to the positions of atoms in the $\text{z = ±}\text{1}\text{4}$ planes of the σ-phase structure. Sequence faults were found in the irregular part of the lattice image. The analysis of the faults shows that an extra plane of $\text{1}\text{2}\text{a}{}_0$ width is inserted into the regular structure and one side of the fault is slightly shifted parallel to the fault plane with respect to the other side, which is consistent with the model proposed by Frank and Kasper. A unit cell step of the sequence faults was found and a model of the step was proposed.     

Preparation of crystalline polyamides by the alternating copolymerization of aziridines and cyclic imides

The copolymerization of aziridines and cyclic imides was studied. Aziridines copolymerized alternately with cyclic imides to give crystalline polyamides. Ethylenimine and succinimide copolymerized to nylon 2,4, melting near 300°C., without any catalyst. Similarly, the corresponding crystalline polyamides were obtained from the systems of 1,2-propylenimine–succinimide, ethylenimine–glutarimide, and ethylenimine–phthalimide. The copolymerization of aziridines and cyclic imides in the presence of BF₃OEt₂ gave a copolymer which was rich in aziridine units, whereas, the addition of triethylamine had no influence on the copolymer composition. A mechanism of copolymerization was proposed based on the facts that N-tetramethylenesuccinamide was obtained by the reaction of pyrrolidine and succinimide, N-acetylethylenimine reacted with acetamide to yield N,N′-diacetylethylenediamine and that the rate of this copolymerization was dependent on the electrophilicity of imide.     

Solvent extraction and spectrophotometric determination of iron(II) with 2,2′-dipyridyl-2-furancarbothiohydrazone

2,2′-Dipyridyl-2-furancarbothiohydrazone (DPFTH) was used for the spectrophotometric determination of trace amount of iron(II) after the extraction process. Iron(II) can be quantitatively extracted with DPFTH in benzene from aqueous solution buffered to 3.0–8.0. The extracted species has absorption maxima at 440, 477, and 738 nm and obeyed Beer's law over the range 0–40 μg of iron in 10 ml at 738 nm. The molar absorptivity at this wave length is 1.17 × 10⁴ liters mole^?1 cm^?1. The proposed method is relatively selective for iron(II) and is satisfactorily applied to the determination of the total iron in natural waters. The proton dissociation constants of the ligand determined spectrophotometrically were pK_a1 = 2.88 and pK_a1 = 6.70 at 25 °C and μ = 0.1.     

Chemistry of organosilicon compounds 118. Novel ring contraction reaction of (η4-1,2-disilacyclohexadiene)iron tricarbonyls

1,1,2,2-Dimethyl-3,6-diphenyl-1,2-disilacyclohexadiene reacts with iron pentacarbonyl or diiron nonacarbonyl to give the corresponding (diene)iron tricarbonyl complex which undergoes novel ring contraction reaction to (η⁴-1,1-dimethyl-2,5-diphenyl-1-silacyclopentadiene)iron tricarbonyl on thermolysis at 160°C. Similar results were observed with 1,1,2,2-tetramethyl-3,4,5,6-tetraphenyl-1,2-disilacyclohexadiene.     

Vinyl polymerization. 413. Polymerization of vinyl monomer initiated by poly(vinylbenzyltrimethyl)-ammonium chloride

The polymerization of vinyl monomer initiated by an aqueous solution of poly(vinylbenzyltrimethyl)ammonium chloride (Q-PVBACI) was carried out at 85°C. Styrene, p-chlorostyrene, methyl methacrylate, and i-butyl methacrylate were polymerized, whereas acrylonitrile and vinyl acetate were not. The effects of the amounts of vinyl monomer, Q-PVBACI, and water on the conversion of vinyl monomer were studied. The overall activation energy in the polymerization of styrene was estimated as 79.1 kJ mol^?1. The polymerization proceeded through a radical mechanism. The selectivity of vinyl monomer was discussed by “a concept of hard and soft hydrophobic areas and monomers.”     

Function of the Reaction Center of Green Sulfur Bacteria

The reaction center (RC) of green sulfur bacteria belongs to the Fe-S type RC, as do the photosystem I of oxygenic photosynthetic organisms and the RC of heliobacteria. The core parts of the green sulfur bacterial and the heliobacterial RC are assumed to be homodimeric, in contrast to those of purple bacteria, photosystem I and photosystem II. This paper describes recent advances in the study of the function of the green sulfur bacterial RC.     

Ionic conductivity of superionic conducting glasses in the pseudobinary system AgIAg2MoO4

The ionic conductivity was measured in the temperature range 250–300 K as a function of composition of superionic conducting glasses in the pseudobinary system AgIAg₂MoO₄. The conductivity, ranging from 10^?2 to 10^?4 Ω^?1 cm^?1 at room temperature, increases linearly in logarithmic scale with increasing AgI content, while the total silver ion concentration remains nearly constant in the whole glass-forming region of the present system. Such a composition dependence of conductivity is considered to be evidence that only a fraction of the silver ions in glass contributes to the ionic conduction. The conductivity and the activation energy for conduction differ slightly between bulk glasses and pressed pellets of pulverized glasses. The close agreement in bulk glasses and pellets suggests that bulk rather than grain boundary or surface diffusion dominates the conduction process in the present glasses.     

Isolation and crystal structure of a water-soluble iridium hydride: a robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds in acidic media

This paper reports the isolation and structural determination of a water-soluble hydride complex [Cp*Ir(III)(bpy)H](+) (1, Cp* = eta(5)-C(5)Me(5), bpy = 2,2'-bipyridine) that serves as a robust and highly active catalyst for acid-catalyzed transfer hydrogenations of carbonyl compounds at pH 2.0-3.0 at 70 degrees C. The catalyst 1 was synthesized from the reaction of a precatalyst [Cp*Ir(III)(bpy)(OH(2))](2+) (2) with hydrogen donors HCOOX (X = H or Na) in H(2)O under controlled conditions (2.0 < pH < 6.0, 25 degrees C) which avoid protonation of the hydrido ligand of 1 below pH ca. 1.0 and deprotonation of the aqua ligand of 2 above pH ca. 6.0 (pK(a) value of 2 = 6.6). X-ray analysis shows that complex 1 adopts a distorted octahedral geometry with the Ir atom coordinated by one eta(5)-Cp*, one bidentate bpy, and one terminal hydrido ligand that occupies a bond position. The isolation of 1 allowed us to investigate the robust ability of 1 in acidic media and reducing ability of 1 in the reaction with carbonyl compounds under both stoichiometric and catalytic conditions. The rate of the acid-catalyzed transfer hydrogenation is drastically dependent on pH of the solution, reaction temperature, and concentration of HCOOH. The effect of pH on the rate of the transfer hydrogenation is rationalized by the pH-dependent formation of 1 and activation process of the carbonyl compounds by protons. High turnover frequencies of the acid-catalyzed transfer hydrogenations at pH 2.0-3.0 are ascribed not only to nucleophilicity of 1 toward the carbonyl groups activated by protons but also to a protonic character of the hydrido ligand of 1 that inhibits the protonation of the hydrido ligand.     

Kinetics of γ-ray polymerization of formaldehyde in the presence of carbon dioxide

A kinetic study of the γ-ray polymerization of formaldehyde in toluene solution in the presence of carbon dioxide was carried out at temperatures of + 13 to ?17°C. Two modes of the polymerization, spontaneous and γ-ray polymerization, occur in this system. The γ-ray polymerization, experimentally separated from the spontaneous polymerization, was investigated. The rate of γ-ray polymerization increased slightly with the square root of carbon dioxide concentration. The rate of polymerization was also found to be proportional to the dose rate and the square of monomer concentration. The molecular weight of polymer formed was independent of the reaction condition. The apparent activation energy was estimated to be 10.3 kcal./mole. The kinetics of the γ-ray polymerization in the presence of carbon dioxide are explained quantitatively by a cationic mechanism, and the role of carbon dioxide is as an action of retardation for neutralization of the cationic initiating species, which was produced by γ-radiation, by means of a reverse reaction with an electron. Physical and mechanical properties of the polymer obtained by γ-ray polymerization were also investigated.     

Ring opening reaction of gem-difluorocyclopropyl ketones with nucleophiles

Syntheses of gem-difluorocyclopropyl ketones (3a–d) and their reactions with nucleophiles are described. Ring opening reactions of 3a,c and d with a methanolate and a thiolate anion took entirely different courses of bond scission of the cyclopropane ring.