bluuebunny/crossref_metadata_2025_split huggingface dataset:
Metal Chelates of Aromatic o,o′-Dihydroxyazo Compounds. I. The Fluorescence Properties of the Metal Chelates of o,o′-Dihydroxyazobenzene and Their Use in Fluorometry
Authors: Hiraki Keiz\={o} 
Published: July 2006

Abstract
As fluorometric reagents for the determination of Al, Ga, In, etc., 11 derivatives of o,o′-dihydroxyazobenzene were examined in an attempt to determine the most desirable structure of azo compounds. o,p,o′-Trihydroxyazobenzene type compounds were more sensitive than o,o′-dihydroxyazobenzene; CH3O-group substitution at the para position was also efficient. The SO3H substitution increased, whereas the Cl substitution decreased the fluorescence of metal complexes, and the CH3-substituted compound did not form fluorescent metal complexes because of its low solubility in water and because of the steric hindrance. Superchrome Garnet Y and Lumogallion seemed to be excellent fluorometric reagents for Al and Ga; 2-(2,4-dihydroxyphenylazo)-1-hydroxybenzene and 3-(2-hydroxy-4-methoxyphenylazo)-4-hydroxybenzene sulfonic acid were also useful. Therefore, the several conditions for the fluorometric determination of Al and Ga with those compounds were also investigated.
The Infrared Spectra and Normal Coordinate Treatments of X3M–Mn(CO)5(X=Cl, Br, and I; M=Si, Ge, and Sn). II.
Authors: Onaka Satoru 
Published: July 2006

Abstract
The infrared absorption spectra (2200–50 cm−1) have been measured for four metal-metal bonded molecules, Cl3Si–Mn(CO)5, Cl3Ge–Mn(CO)5, Br3Ge–Mn(CO)5, and I3Sn–Mn(CO)5. Vibrational normal coordinate analyses have been made for each of these molecules on the basis of a modified Urey-Bradley force-field. The calculated frequencies agree closely with validly-assigned frequencies. The metal-metal stretching force constant, K(M–Mn), or the F-matrix element, f(M–Mn), varies with the halogen atom, and increases as the electronegativity of X increases. The force constant, K(M–Mn), or f(M–Mn) depends also on the IVb metal atom, and increases in the order of: K(Si–Mn)≥K(Ge–Mn)&gt;(Sn–Mn), or f(Si–Mn)≥f(Ge–Mn)&gt;f(Sn–Mn). However, there is no clear relationship between the electronegativity of M and the K(M–Mn) or (M–Mn). These dependences of K(M–Mn) or f(M–Mn) on X and M are discussed, along with the bonding implications of the M–Mn bonds, on the basis of the sets of the force constants, or the sets of the F-matrix elements, and are interpreted in terms of the predominant σ-bonding framework of the M–Mn bonds.
The Kinetics of Oxygen Exchange between Arsenate Ions and Solvent Water
Authors: Okumura Akiko , Okazaki Nobukazu 
Published: July 2006

Abstract
The rates of oxygen exchange between arsenate ions and water have been measured at 14.5 °C and 30 °C over the pH range of 6.5–12.5. The rate, R, may be expressed by the rate law:
R=k_1[H_2AsO_4^-]+k_2[HAsO_4^2-]+k_3[AsO_4^3-]+k_4[H_2AsO_4^-]^2+k_5[H_2AsO_4^-][HAsO_4^2-]+k_6[HAsO_4^2-]^2.
The exchange rates at 30 °C and I=0.55 have been analyzed in terms of this rate law to obtain the values of the rate constants, k1–k6. The activation energy of the over-all exchange reaction is 13.2±0.2 kcal/mol at pH 7.51 and 22.14±0.02 kcal/mol at pH 9.79. The reaction shows a negative salt effect in the region of pH 7.5, and a positive salt effect at pH 9.3.
The Effects of Doubly-excited Configurations in the P-P-P-CI Calculation
Authors: Shinoda Hiroyuki , Tatematsu Hidenobu , Miyazaki Tomoo 
Published: July 2006

Abstract
The effects of doubly-excited configurations, especially of the χk1mn type, on the results of P-P-P-CI calculations of unsaturated compounds have been discussed by comparing the results obtained by three different types of CI treatment. The calculations of the pi-electronic total energies of ground states, the electronic transition energies, the oscillator strengths, and the pi-electronic densities of sixteen molecules were performed. The core resonance integrals and electronic repulsion integrals were readjusted so that the transition energies, obtained by CI calculations considering all the singly- and doubly-excited configurations, might coincided with the experimental results. From the results of these calculations, it is found that χk1mn-type configurations play an important role in CI calculation.
Calorimetric Study of the Glassy State. VIII. Heat Capacity and Relaxational Phenomena of Isopropylbenzene
Authors: Kishimoto Koji , Suga Hiroshi , Seki Syûzô 
Published: July 2006

Abstract
The heat capacities of isopropylbenzene were measured with an adiabatic calorimeter for the crystal from 14 to 177.13 K (Tm), for the glassy state from 14 to around 126 K (glass transition temperature: Tg) and for the liquid from Tg to 313 K, with a sample of 99.93% purity. The heat and entropy of fusion were found to be 7326 J mol−1 and 41.36 J K−1 mol−1, respectively. Based on these data, a set of thermodynamic functions are tabulated at rounded temperatures. In addition to the primary glass transition phenomenon, a secondary enthalpy relaxation as well as a step-like heat capacity anomaly was observed at around 70 K. These facts were discussed in correlation with the β-relaxation already observed by dielectric measurement. Gonfigurational entropies of the supercooled liquid and of the glassy state were calculated to investigate a relation with relaxational properties. The agreement is found between the temperatures where catastrophe occurs in viscosity (T0), and where the configurational entropy vanishes (T2). Finally, a kind of heat capacity break observed in the liquid state is discussed against the view that this behavior is compatible with a third-order thermodynamic transition.
The Electrification of Iron Oxide in Water
Authors: Morimoto Tetsuo , Kittaka Shigeharu 
Published: July 2006

Abstract
The electrification of iron oxides pretreated at various temperatures from 600 to 1200 °C has been investigated in water by measuring the ζ-potential as a function of the pH. From the surface-chemical point of view, iron oxides pretreated at temperatures lower than 800 °C behave differently from those pretreated at higher temperatures ; the isoelectric point of the former samples reaches an equilibrium value in a few hours, while that of the latter samples increases slowly to an equilibrium value with an increase in the surface hydration. On the other hand, the equilibrium isoelectric point of iron oxide decreases sharply upon heat treatment at 800–1000 °C, corresponding to the change in the chemical composition of iron oxide from Fe2O3 to Fe3O4.
The Alkylation of 3,5-Dimethylisoxazole
Authors: Kashima Choji , Tobe Shinji , Sugiyama Noboru , Yamamoto Makoto 
Published: July 2006

Abstract
3,5-Dimethylisoxazole (1) was alkylated with sodium amide in liquid ammonia to give 3-methyl-5-alkylisoxazoles. By di- and tri-alkylation reactions using excess sodium amide, isoxazoles having secondary and tertiary alkyl groups at 5-position could be obtained. The hydrogenolysis and hydrolysis of these isoxazoles were also studied.
Kinetic Studies of the Nickel Lactate Complex Formation in Solution by the Pressure-jump Method
Authors: Harada Shoji , Tanabe Hideyuki , Yasunaga Tatsuya 
Published: July 2006

Abstract
The nickel lactate complex formation reaction in an aqueous solution was studied by the pressure-jump method and the overall rate constants, the stability constants, and the activation parameters were determined. The results were interpreted by the use of the step-by-step complex formation mechanism, and it was revealed that the rate-determining step is the chelate-ring formation process. The ligand effect on the rate of the complex formation was also considered.
Catalytic Decomposition of Stable Sulfur Ylids
Authors: Matsuyama Haruo , Minato Hiroshi , Kobayashi Michio 
Published: July 2006

Abstract
In the presence of dimethoxy disulfide, such stable sulfur ylids as Me2S+–C−(COOMe)2, Me2S+–C−(CN)2, and Me2S+–C−HCOPh were found to decompose at 35 °C, forming methyl sulfide and an olefin or a cyclopropane. Thiocyanogen and trifluoromethyl disulfide were found to possess similar catalytic activity. The scope and mechanism of these reactions are discussed.
The Reflection Spectra of Simple Salts of the Tetracyanoquinodimethane Anion Radical
Authors: Oohashi Yukako , Sakata Tadayoshi 
Published: July 2006

Abstract
The reflection measurements were carried out for fourteen simple salts of the tetracyanoquinodimethane (TCNQ) anion radical over the range from 5000 to 42000 cm−1 by Avery’s method. The solid-state spectra show three bands (CT, YI, and YII) and exhibit distinct differences depending on the cation species. According to the differences in the transition energy (σi) and the oscillator strength (fi), the fourteen salts were classified into three groups (A, B, and C). The solid-state spectra of Group A resemble that of the dimer in an aqueous solution. Group B is characterized by the red shift of the CT band and the intensity increase in the YII band. The spectra of Group C exhibit a vibrational structure in the YI band which is similar to the monomer spectrum in an aqueous solution. Moreover, the large dispersion of the refractive index and the intensity increase in the bands of local excitation were observed for Group C. The electronic structures of these groups were studied by the use of the composite-system method. By taking account of the crystal structure of RbTCNQ-I, belonging to Group A, the stabilization energy (J*) of the ground state was calculated from σCT and fCT. The J* values for ten salts in Group A correspond well to the singlet-triplet separation in the ground state observed by ESR measurements.
The Electronic Spectrum of p-Benzosemiquinone Anion in Aqueous Solution
Authors: Fukuzumi Shun-ichi , Ono Yoshio , Keii Tominaga 
Published: July 2006

Abstract
The electronic spectrum of p-benzosemiquinone anion in aqueous solution formed through the oxidation of hydroquinone with manganese dioxide was measured at room temperature. The absorption maxima were found at 430, 404, and 316 mμ with shoulders at 371 and 310 mμ. It was confirmed that these absorption maxima are due to the same species p-benzosemiquinone anion, on the ground that their kinetic behaviors are the same. The molar extinction coefficients of the absorption maxima and the oscillator strengths of the absorption bands were estimated.
Dielectric Relaxation and Molecular Structure. VII. Structure of the Molecules of Diphenylene Dioxide Type
Authors: Koga Yoshinori , Takahashi Hiroaki , Higasi Keniti 
Published: July 2006

Abstract
The dielectric constants and losses of diphenylene dioxide, phenoxathiin, thianthrene, xanthene and pheno-thiazine have been measured in dilute solution of benzene at the millimeter-wave frequency of 100 GHz at 20 °C. Diphenylene dioxide is found to have a very small dielectric relaxation time which is associated with the change in dipole orientation by the intramolecular change (butterfly motion). The dipole moment of this molecule is small but not considered to be zero. Similar to thianthrene, which has a folded structure about the S–S axis, diphenylene dioxide is also folded about the O–O axis or can easily have a folded structure. Phenoxathiin and the other two molecules have a folded structure and the dielectric relaxation times (at 100 GHz) reveal the effect of the butterfly-flapping motion associated with the barrier height for this internal motion.
Radical Formation Initiated by the Biphotonic Excitation of Acridone
Authors: Miyashita Yoshikatsu , Niizuma Shigeya , Kokubun Hiroshi , Koizumi Masao 
Published: July 2006

Abstract
The photochemical formation of alcohol radical has been found to occur in the rigid solvent of ethanol (77 K) and in the polyvinyl alcohol (PVA) film (77 K and at room temperature), when acridone is dissolved as a sensitizer. It has been established that by absorbing two photons stepwise acridone gives rise to radicals which abstract hydrogen atoms from alcohol molecules, this being called the radical reaction mechanism and abbreviated as R-R mechanism. The energies necessary for the radical formation were estimated by determining energy levels of acridone and examining the wavelength dependence of the reaction. They differed for ethanol (77 K), PVA (77 K) and PVA (room temp.), perhaps due to the cage effect. The feature of the R-R mechanism has been compared with that of the energy transfer type (E-T mechanism) in which the energy is transferred from the higher triplet of solute to solvent molecules. When methyl iodide with a lower dissociation energy is added to an ethanol solution of acridone (77 K) and is then irradiated by an exciting light ineffective for R-R mechanism, methyl radical is formed by E-T mechanism. When the two types of reaction were energetically possible, E-T mechanism occurred more easily than R-R mechanism.
The Preparation and Absorption Spectra of the Mixed cis-Dicyano Complexes of Cobalt(III) with Carbonato or Related Ligands
Authors: Fujinami Shuhei , Shibata Muraji 
Published: July 2006

Abstract
By the reaction of the [Co(CO3)3]3− complex and KCN, the complex anion, [Co(CN)2(CO3)2]3−, has been isolated as the tris(ethylenediamine)cobalt(III) salt. From this dicarbonato-complex anion, related dicyano complexes, [Co(CN)2(CO3)(C2O4)]3− and [Co(CN)2(C2O4)2]3− have then been obtained as Λ(+)589-[Co(en)3]3+ salts, with resolutions into the active forms. Other related complexes, [Co(CN)2(dtc)2]− and [Co(CN)2(xan)2]−(dtc=dimethyldithiocarbamate anion, xan=methylxanthate anion), have also been prepared as potassium salts from the dicarbonato complex. The absorption spectra of all of the dicyano complexes have been measured, as have the CD spectra of the resolved dicyano complexes. Based on these spectral data, the geometrical structures of all the dicyano complexes have been identified as of the cis form. The [Co(CN)(malo)2OH2]2− complex has been isolated as potassium salt. From the PMR spectrum, the structure has been determined as the trans form. The polarized spectra of a crystal of this complex have also been measured.
Layered Compounds. XV. Synthesis and Properties of Multilayered Cyclophanes
Authors: Otsubo Tetsuo , Mizogami Shigeyoshi , Otsubo Ikuko , Tozuka Zenzaburo , Sakagami Akiko , Sakata Yoshiteru , Misumi Soichi 
Published: July 2006

Abstract
A series of multilayered cyclophanes up to sixfold were synthesized by 1,6-Hofmann elimination method. Odd layered and some dissymmetric ones were derived by means of cross-breeding pyrolysis of mixed quaternary ammonium hydroxides. The electronic spectra, absorption, emission, and CT absorption of charge-transfer complexes, of these cyclophanes exhibited remarkable transannular π-electronic interaction among chromophores closely stacked by methylene bridges. The interaction is increased eminently when the layer is varied from single to quadruple, but becomes less effective from quadruple to fivefold and no longer appreciable for more than fivefold one.
Application of the Mannich Reaction to 1-Azaazulan-2-one. Syntheses of Seven-Membered Analogues of Tryptophan and Related Compounds
Authors: Sato Akira , Nozoe Shigeo , Toda Takashi , Seto Shuichi , Nozoe Tetsuo 
Published: July 2006

Abstract
Application of the Mannich reaction to 1-azaazulan-2-one (I) gave 3-dimethylamino-1-azaazulan-2-one (III) in a good yield. Tryptophan analogue and related compounds having this structure (I) were synthesized by the reactions of the quaternary base (VI) of III with potassium cyanide and diethyl acetylaminomalonate. Also, some other reactions of III and VI are reported.
The Polymerization of α-Naphthylmethylvinylether and 3-Pyrenylmethylvinylether and Electrical Conductivity of Their Polymers
Authors: Yoshimoto Shigeki , Okamoto Kenichi , Hirata Hirotaka , Kusabayashi Shigekazu , Mikawa Hiroshi 
Published: July 2006

Abstract
A new vinylmonomer with a large pendant π-electron group was synthesized. α-Naphthylmethylvinylether and 3-pyrenylmethylvinylether were polymerized in good yields, although their polymers have fairly low molecular weights. Both polymers have a fairly high isotacticity. Poly-3-pyrenylmethylvinylether showed a large photocurrent in its absorption region and a small photocurrent even above 500 to 1000 mμ. The doped TCNE significantly sensitized its photoconductivity.
Polarized Absorption Spectra of Single Crystals of Ion Radical Salts. III. Temperature Dependence of the Crystal Spectra of Potassium-Chloranil
Authors: Hiroma Shoji , Kuroda Haruo 
Published: July 2006

Abstract
The polarized absorption spectra in the 10000–37000 cm−1 region were observed on the single crystal of the water-free modification of the potassium-chloranil salt, K+·(chloranil)−, by using a microspectrophotomer, and the variation of the spectra with temperature was examined. The crystal gives a near-infrared absorption band associated with the charge transfer between chloranil radical anions, the maximum of which is located at 11.5×103 cm−1. The absorption bands in the 20000–37000 cm−1 region were assigned to the local-excitation bands associated with the transitions in the chloranil anion. The intensity of the charge-transfer band gradually increases on lowering the temperature. An abrupt increase of intensity occurrs in the charge-transfer band at the phase-transition point. There is a close correlation between this change and the temperature dependence of the paramagnetic susceptibility of the salt.
The Photo-Erasable Memory Switching Effect of Ag Photo-Doped Chalcogenide Glasses
Authors: Shimizu Isamu , Kokado Hiroshi , Inoue Eiichi 
Published: July 2006

Abstract
The electric conductivity of the chalcogenide glass increased with an increase in the amount of Ag which had been photo-doped. By applying the electric field to the electrodes which were set on the surface of the Ag photo-doped chalcogenide glass film, a conductive path was grown from the cathode to the anode. As a result of the connection of the electrodes with the path, the electric resistance of the cell abruptly decreased (ON state). The path was made of the metal silver reduced by electrolysis and was diminished by irradiation with light. As the path was erased, the cell was turned into the resistant state (OFF state). The cycles were repeatable many times. There was a delay time (td) in turning the cell from the OFF to the ON state by applying the electric field (E). It was empirically described by the following equation for the Ag photo-doped chalcogenide glasses:
t_d=aexp(-b·E)
The Cadmium-photosensitized Decomposition of Acetaldehyde, Propionaldehyde, and n-Butyraldehyde
Authors: Yamamoto Koji , Tsunashima Shigeru , Sato Shin 
Published: July 2006

Abstract
The reactions of acetaldehyde, propionaldehyde, and n-butyraldehyde photosensitized by cadmium (3P1) have been investigated at 270 °C. The pressure dependence of the main products, CO, RH (R=CH3, C2H5, and n-C3H7) and R2, was well explained by the following reaction mechanism; Cd*+RCHO→R+CHO+Cd or RH+CO+Cd. R+RCHO→RH+RCO, RCO→R+CO, CHO→H+CO, H+RCHO→H2+RCO, R+R→R2 or RH+ Olefin. Carbon dioxide was found to be a rather good quencher for triplet cadmium atoms, and was used for estimating the relative quenching efficiencies of the three aldehydes and acetone. The values obtained were 0.16, 1.0, 1.3, 1.2, and 1.4, respectively for carbon dioxide, acetone, acetaldehyde, propionaldehyde, and n-butyraldehyde, when the efficiency of cis-2-butene was assumed to be unity.
Far Infrared and Raman Spectra of K3[Co(CN)6] and [Co(NH3)6][Co(CN)6]
Authors: Nakagawa Ichiro 
Published: July 2006

Abstract
Far infrared spectra of K3[Co(CN)6] and [Co(NH3)6][Co(CN)6] and a single crystal Raman spectrum of K3[Co(CN)6] have been measured. Calculations of optically active crystal vibration frequencies have been made, on the basis of the crystal structure determined precisely. For these two types of established crystal structures (C2h5 for K3[Co(CN)6] and C3i2 for [Co(NH3)6]) [Co(CN)6] of hexacyano-complex salts, lattice frequencies have been determined. For [Co(NH3)6][Co(CN)6] the mean amplitudes of two kinds of cobalt atoms have been calculated and compared with those obtained by Iwata and Saito assuming that both complex ions behave as a rigid body.
Copper(II) Complexes with Some Aliphatic Diaminealcohols
Authors: Ishimura Yasuo , Nonaka Yasuomi , Nishida Yuzo , Kida Sigeo 
Published: July 2006

Abstract
Copper(II) complexes were prepared with a series of tridentate ligands, NH2(CH2)mCHRNH(CH2)n OH (R=H or CH3; m=1 or 2; n=2 or 3). Compounds obtained can be classified into three groups: (1) CuLCl2, (2) CuL(ClO4) and (3) CuL2X2, (L and L′ represent the neutral and the anionic ligands, respectively, and X denotes Cl or ClO4). (1) and (3) were found to be mononuclear in which L functions as a bidentate ligand donating with the two nitrogen atoms. (2), except for the complex with L′=NH2(CH2)3NH(CH2)2O− have the binuclear structure with alkoxo bridges. The absorption bands at about 350 nm are characteristic of the binuclear structure with alkoxo or hydroxo bridges.
Stability of Fused Rings in Metal Chelates. XI. Stability of Dipeptide Amide-Copper(II) Complexes
Authors: Yamauchi Osamu , Nakao Yasuo , Nakahara Akitsugu 
Published: July 2006

Abstract
The structure-stability relationship between the copper(II) complexes of several dipeptide amides consisting of glycine and/or β-alanine has been investigated by potentiometric titration. The amides of glycylglycine, glycyl-β-alanine, and β-alanylglycine (abbreviated as H2L) have been found to form complexes of the type Cu(H2L)2+ with logK1 values 4.80–5.22. The −logKC1 values for deprotonation of the peptide group are 5.05–5.42 and comparable to those of tripeptides, whereas the −logKC2 values for the terminal amide group are 7.96 for glycylglycine amide and 8.99 for glycyl-β-alanine amide. This indicates that, at neutral pH, the –CONH2 group coordinates to copper(II) mainly through the carbonyl oxygen. β-Alanyl-β-alanine amide-copper(II) system gave precipitates at an early stage of titration. The structures and relative stability of the complexes of types Cu(H2L)2+, Cu(HL)+, and CuL have been discussed from comparative studies of their stability constants.
The Analytical Application of Sulfur Analogues of β-Diketones. III. The Separation of Cobalt(II), Nickel(II), Copper(II), Zinc(II), Mercury(II), Lead(II), and Cadmium(II) as Their STTA (1,1,1-Trifluoro-4-(2-thienyl)-4-mercapto-3-buten-2-one) Complexes by Thin-layer Chromatography on Silica Gel
Authors: Honjo Takaharu , Kiba Toshiyasu 
Published: July 2006

Abstract
Cobalt(II), nickel(II), copper(II), zinc(II), mercury(II), lead(II), and cadmium(II) were extracted with STTA (1,1,1-trifluoro-4-(2-thienyl)-4-mercapto-3-buten-2-one) in cyclohexane, and their colored complexes were chromatographed on a thin-layer of silica gel with various organic solvents. The developing solvents used were 18 kinds of pure solvents and 10 different binary solvent mixtures of 1 :1, v/v. An excellent separation could be achieved after development with carbon tetrachloride, carbon disulfide, ethyl acetate, and cyclohexane–chloroform, chloroform–carbon disulfide, and carbon tetrachloride–carbon disulfide mixtures. The Rf value generally increased in the following orders: Cd(II), Zn(II), Pb(II), (STTA)&lt;Hg(II)&lt;Co(II, III)&lt;Cu(II)&lt;Ni(II) (with carbon tetrachloride); Cd(II), Zn(II), Pb(II), (STTA)&lt;Co(III)&lt;Hg(II)&lt;Cu(II)&lt;Ni(II) (with carbon disulfide); Cd(II), (STTA)&lt;Zn(II)&lt;Pb(II)&lt;Hg(II), Co(III), Cu(II), Ni(II) (with ethyl acetate); and Cd(II), Zn(II), Pb(II), (STTA)&lt;Hg(H)&lt;Co(III)&lt;Cu(II)&lt;Ni(II) (with the cyclohexane-chloroform, chloroform-carbon disulfide, and carbon tetrachloride–carbon disulfide mixtures). A few μg Ni(STTA)2 chelates on the plate could be determined quantitatively by measuring the spot area from the curve drawn on a millimeter-graph sheet after driving a densitometer across the spot. Some aspects of the behavior of the STTA chelates on the thin-layer of silica gel have also been discussed.