bluuebunny/crossref_metadata_2025_split huggingface dataset:
Magnetic Properties and Low-Field ESR of Organic Free Radicals, Monochloroporphyrexide and Porphyrexide
Authors: Yoshioka Toshio 
Published: July 2006

Abstract
The static magnetic susceptibility, and ESR and proton NMR spectra of powder samples of monochloroporphyrexide were measured above 1 K and compared with those of porphyrexide. A broad maximum in the static susceptibility of monochloroporphyrexide, indicating an antiferromagnetic interaction, appeared at 22.5 K. The relative susceptibilities of the two radicals obtained from the ESR signal intensities and the proton NMR shifts agree qualitatively with the static susceptibilities. In the low-field ESR spectra (135 MHz) of each radical, broadening of the g=2 absorption line and distinct appearance of the g=4 absorption line were found in the temperature region below Tm, the temperature at which the susceptibility is maximum. The anisotropy of the g-value was estimated from Q-band ESR spectra. Furthermore, the unpaired electron-spin distribution over the ring was estimated from the X-band ESR and the proton NMR spectra. The results are interpreted assuming that the magnetic behavior of the two radicals is due to alternating antiferromagnetic Heisenberg linear chains with alternating parameters, a=0.4 and a=0.6, respectively.
The Raman Spectra of Solid and Liquid Tetramethylsilane
Authors: Shinoda Takako 
Published: July 2006

Abstract
Laser Raman spectra of tetramethylsilane in its three crystalline forms and in the liquid state have been observed for the lattice and intramolecular vibrational regions. The bands due to lattice vibrations increase as the transitions from α to β and to γ occur. The spectra of the β and γ forms exhibit crystal-field splittings of intramolecular bands. The observed spectra suggest that the β and γ forms are isomorphous with each other and the α form has a higher symmetry.
Large-Area (600 mm2) Bimolecular Film in Aqueous Solutions. The Effect of an Amine–Ni2+ Complex on the Stability of cis-9-Octadecenylamine Bimolecular Film
Authors: Yoshida Tadayoshi , Okuyama Masataka , Itoh Takahiro 
Published: July 2006

Abstract
A large, planar, bimolecular film (bilayer, 600 mm2) of cis-9-octadecenylamine (oleylamine) was found to be formed in an NiCl2 solution. From the effect of the added metal ions on the proton magnetic resonance spectrum of octadecenylamine, it appears that the complex between the octadecenylamine molecule and the metal ion increases the stability of the bilayer. The thickness of the bilayer depended strongly on the kind of solvent in the filmforming solution. When decane, a normal alkane solvent, was used, the thickness of the bilayer was greatest (4.6 nm), and the temperature effect was smallest. The experimental results are explained in terms of (i) the influence of the solvent on the conformation of the octadecenyl chain and (ii) the amount of solvent remaining in the film.
A CNDO-type MO Method of the Third Transition Metal Complexes and the Electronic Structure of Methylmercury(II) Halides
Authors: Sakaki Shigeyoshi , Hagiwara Nobuo , Iwasaki Noriko , Ohyoshi Akira 
Published: July 2006

Abstract
The parameters of a CNDO-type SCF-MO method are determined for some 5d transition metal complexes such as IrCl63−, AuCl4−, and HgCl42− by comparing the calculated transition energies of these complexes with their experimental values. MO calculations with these established parameters are also carried out for IrBr63−, AuBr4−, HgX42−, HgX2, and CH3HgX (X=Cl, Br, and I). The transition energies and assignments obtained from MO calculations are in fair agreement with experimental ones, with a few exceptions. This MO method gives successful results for the electron density and the bond strength: (1) a linear relation is obtained between the calculated and observed net charges on the Hg atom of HgX2 and CH3HgX, and (2) similar linear relations are obtained between the bond index EM–X values and the stretching force constant fM–X and between the EHg–C value and the fHg–C. Some discussion is presented for the Hg–C bonding character of the CH3HgX; the Hg–C bond is mainly contributed from the covalent interaction of the 6s and 6p orbitals of the Hg atom with the 2s and 2p orbitals of the C atom. The contributions of the Hg 5d orbitals and the electrostatic interaction are rather small.
Studies on Mixed Chelates. VI. Mixed Copper(II) Chelates with N,N,N′,N′-Tetraethylethylenediamine and Various β-Diketones
Authors: Fukuda Yutaka , Miura Yukiko , Sone Kozo 
Published: July 2006

Abstract
Ten new mixed copper(II) chelates containing N,N,N′,N′-tetraethylethylenediamine and various β-diketones were prepared and the cause of the large variations of νmax values observed in the visible absorption spectra of their organic solutions was discussed in comparison with similar variations of the corresponding tetramethyl chelates.
Conductance of Some High Valence Type Electrolytes in Mixed Solvents. II. Conductance of Pentaamminenitrocobalt(III) and Tris(1,10-phenanthroline)iron(II) Sulfates in Water–Ethylene Glycol Mixtures at 25 °C
Authors: Kubota Eiji , Yokoi Masatoki 
Published: July 2006

Abstract
Conductance data are reported for dilute solutions of pentaamminenitrocobalt(III) sulfate, [Co(NO2)(NH3)5]SO4, and tris(1,10-phenanthroline)iron(II) sulfate, [Fe(phen)3]SO4 in water–ethylene glycol mixed solvents at 25 °C. The conductance data were analyzed in terms of the 1957 Fuoss-Onsager and Fuoss-Hsia equations. While the application of the 1957 Fuoss-Onsager equation to [Fe(phen)3]SO4 data suggested a complete dissociation of the salt over the entire range of solvent compositions, the Fuoss-Hsia equation fitted the data better and yielded KA values which are in accord with the ion association theories. [Co(NO2)(NH3)5]SO4 had a higher association constant in the range of solvent composition studied (0 to 40% ethylene glycol) than the predictions of the ion association theories.
ESR of Hot Ions: Low Spin Pt(III) Complex Ions Produced by γ-Irradiation
Authors: Amano Chikara , Fujiwara Shizuo 
Published: July 2006

Abstract
Tervalent platinum complex ions have been observed by the electron spin resonance method upon γ-irradiation of both bivalent and quadrivalent complexes. From their g-values, the tervalent complex ions can be classified into two types, one axially symmetric and the other rhombic, the former having typical g-values of 2(g⁄⁄) and 2.4(g⊥), and the latter a g1-value slightly lower than the free electron value of 2.0023. It has been shown by means of ligand field theory that both types have 5d7 low spin electron configuration. The hyperfine interaction due to 195Pt is one order of magnitude larger than that in cobalt complexes with 3d7 low spin configuration, indicating that the configuration interaction involving 6s-orbital is more important than that for 3d transition metal complexes involving 4s-orbital, and that 5d electrons penetrate deeply into inner shells, resulting in core polarizarion.
The Effect of NCS− on the Radiation-induced Decoloration of Azo and Anthraquinone Dyes in N2O-saturated Aqueous Solutions
Authors: Suzuki Nobutake , Hotta Hiroshi 
Published: July 2006

Abstract
The radiation-induced decoloration of azo and anthraquinone dyes was studied in N2O-saturated aqueous solutions containing NCS−. In the N2O-saturated solutions, the decoloration yield, G(–Dye), increased markedly upon the addition of NCS−, which is an efficient scavenger of the OH radical—that is, from 1.46 up to 2.10 for Acid Red 265 and from 0.51 up to 1.51 for Acid Blue 40 upon the addition of 1 mM NCS−. In the nitrogen-saturated solutions, however, the G(–Dye) decreased upon the addition of NCS−. It is concluded that the increase in the G(–Dye) upon the addition of NCS− in the N2O-saturated solutions is mainly attributable to the attack of the radical anion (NCS)2− on the ring structure of the dyes. This radical anion is formed through the following path: NCS−+OH→NCS+OH− and NCS+NCS−\ightleftarrows(NCS)2−. At low NCS− concentrations, the G(–Dye) decreased for Acid Red 265 and increased for Acid Blue 40. This may be attributable to the larger reactivity of (NCS)2− on Acid Blue 40 than on Acid Red 265.
Charge-Transfer Absorption of Solid Ion Radical Salts, Application of One-Dimensional Hubbard Model
Authors: Iida Yôichi 
Published: July 2006

Abstract
The electronic spectrum of solid ion radical salt is known to be different from the monomer spectrum of the radical ion and to show an intermolecular charge-transfer band in the low-energy region. In order to understand the character of this charge-transfer absorption, one-dimensional Hubbard model was applied to such solid ion radical salt. The transition energy and the theoretical line shape of the charge-transfer absorption were derived and were compared with those of certain TCNQ, anion radical salts.
Formation of CN(B2Σ+) in the Reaction of Acetonitrile with Metastable Ar(3P2,0) Atoms
Authors: Suzuki Kaoru , Kuchitsu Kozo 
Published: July 2006

Abstract
A flowing-afterglow method was applied to the formation of CN(B2Σ+) from CH3CN by impact of metastable argon atoms, Ar(3P2,0). Emission spectra of CN B2Σ+-X2Σ+ (violet band) were analyzed to estimate the energies distributed to the vibrational and rotational motions of CN(B2Σ+). In comparison with the CN(B2Σ+) produced from HCN under similar experimental conditions, relative populations in excited vibrational states are smaller. The effective rotational temperatures range from 5000±1000 K (v=0–2) to 2000±1500 K (v=5–10). An intensity anomaly caused by the rotational perturbation with A2II is used for estimating the ratio of the formation rates of CN B2Σ+ and A2Π, FB/FA, to be 0.19±0.05.
Ionic Equilibria in Mixed Solvents. XII. Hydrolysis of Cadmium(II) Ion in Dioxane–Water and Methanol–Water Mixtures
Authors: Matsui Haruo , Ohtaki Hitoshi 
Published: July 2006

Abstract
The hydrolytic reactions of cadmium(II) ions were studied at 25 °C in dioxane–water and methanol–water mixtures with varying compositions of the organic solvents, each mixture containing 3 mol dm−3 (Li)ClO4 as an ionic medium. Emf measurements were carried out over the range of the total cadmium(II) concentrations of 0.2 to 0.8 mol dm−3 in all the systems. Two complexes Cd2OH3+ and CdOH+ were found in the dioxane–water mixtures, but the latter complex was not detected in the methanol–water system. The formation constant of the Cd2OH3+ complex was slightly larger in the methanol–water mixtures than in the dioxane–water mixtures at the same mole-fraction concentration of the organic solvents.
Reactions of Aminoalkanols with Some Copper(II) Complexes of the Mixed and Non-mixed Bis(Schiff base) Ligands
Authors: Mohankumar V B , Thaker B T , Kohli Rakesh K , Bhattacharya P K 
Published: July 2006

Abstract
Reactions of aminoalkanols have been carried out with mixed and non-mixed bis(Schiff base) complexes of copper(II). In these reactions one of the ligands combines with the aminoalcohol forming a tridentate ligand, wheras another ligand is removed. From the resulting complexes the tendency to form the Schiff base is found to be in the order 2-hydroxybenzophenone≈2-hydroxy-1-naphthaldehyde&gt;salicylaldehyde&gt;2-hydroxyacetophenone. The complexes formed have been characterized by analytical, spectral, and magnetic studies.
Lead(II) Butanedioate–Pentanedioate Mixed Complexes
Authors: Baghel S C , Choudhary K K , Gaur J N 
Published: July 2006

Abstract
Butanedioate and pentanedioate form 1 : 3 highest complexes separately with lead (II) in aqueous medium, three mixed complexes of these two ligands with the metal ion expected in solution being observed. The formation constants of mixed complexes have been evaluated on the basis of polarographic measurements by the method of Schaap and McMasters. The formation constants of the mixed complexes [Pb(X)(Y)]2−, [Pb(X)(Y)2]4−, and [Pb(X)2(Y)]4− are 3.57, 4.22, and 4.49 respectively in their logarithmic form at 303 K, where X2− and Y2− stand for butanedioate and pentanedioate ion, respectively. The statistically calculated values of logarithm of formation constants are 3.43, 4.43, and 4.49 in the above order. The small differences in the observed and calculated values may be due to electrostatic, steric etc. factors. The relative probability of the existence of these mixed complexes and also simple complexes has been explained.
Isolation of Enammonium Salt and Its Rearrangement to the Corresponding Iminium Salt
Authors: Matsushita Hajime , Tsujino Yasuko , Noguchi Masao , Yoshikawa Sadao 
Published: July 2006

Abstract
Enammonium salt of 2-methyl-1-(β-methylstyryl)piperidine (1) was isolated for the first time and characterized. The enammonium salt, 2-methyl-1-(β-methylstyryl)piperidinium chloride (2), was found to change easily to the corresponding iminium salt, 2-methyl-1-(2-phenylpropylidene)piperidinium chloride (3), at room temperature. The structure of the salts derived from 1-(β-methylstyryl)piperidine (4), 2-methyl-1-(β-methyl-styryl)pyrrolidine (5), 1-(β-methylstyryl)pyrrolidine (6), 1-(2-methyl-1-propenyl)pyrrolidine (7), and 2-methyl-1-(2-methyl-1-propenyl)piperidine (8) were also examined.
Direct Synthesis of Methyl Isobutyl Ketone by Reductive Aldol Condensation. III. Kinetics
Authors: Watanabe Yoshiaki , Okada Masato , Izumi Yusuke , Mizutani Yukio 
Published: July 2006

Abstract
The kinetics of the direct catalytic conversion of acetone and hydrogen into methyl isobutyl ketone (MIBK) were investigated in the liquid phase using palladium–zirconium phosphate as a catalyst. Kinetic studies on the conversion of acetone into mesityl oxide (4-methyl-3-pentene-2-one) and its hydrogenation were separately carried out using the same catalyst. It was found that the direct reaction proceeded via a sequence of processes: mesityl oxide was first formed by condensation of acetone on acid sites of the catalyst and MIBK was then produced by hydrogenation of the mesityl oxide on palladium metal in the catalyst. Moreover, the experimental results were well interpreted by assuming that the condensation of acetone was controlled by a surface reaction between the acetone molecules adsorbed on the catalyst surface and that the rate of hydrogenation of mesityl oxide was determined by a surface reaction between dissociated hydrogen atoms and adsorbed mesityl oxide molecules.
Studies on Mixed Chelates. VII. Mixed Nickel(II) Chelates Containing N,N′- or N,N′-Dialkylethylenediamines and Acetylacetone
Authors: Nguyen Thi Nga , Fukuda Yutaka , Sone Kozo 
Published: July 2006

Abstract
Twelve mixed nickel(II) chelates with N,N′- or N,N-dimethyl (or diethyl)ethylenediamines and acetylacetonate ion (acac) were prepared, and their properties were compared with those of the similar chelates with N,N,N′,N′-tetramethyl(or tetraethyl)ethylenediamine. With the decrease of the number and bulkiness of the N-alkyl groups in the diamine, the tendency of forming 6-coordinated mixed chelates remarkably increases. The chelates of the type [Ni(diamine) (acac)]X, formed when X is B(Ph)4, which are essentially similar to the corresponding chelates with N,N,N′,N′-tetraalkylethylenediamines, but more apt to combine with solvent molecules and to go over into 6-coordinated structures than the latter.
Chemistry of 1,3-Glycol Derivatives. II. Lithium Aluminium Hydride and Meerwein-Ponndorf-Verly Reductions of 6,6-Dimethylspiro[2.5]octane-4,8-dione
Authors: Itoh Osamu , Okita Tsutomu , Umezu Makoto , Inoue Masashi , Ichikawa Katsuhiko 
Published: July 2006

Abstract
Lithium aluminium hydride reduction of 6,6-dimethylspiro[2.5]octane-4,8-dione in tetrahydrofuran gave cis- and trans-6,6-dimethylspiro[2.5]octane-4,8-diols. Almost the same ratio of cis: trans=1:2 was obtained with various substrate-reagent ratios. In the case of Meerwein-Ponndorf-Verly reduction, however, cis-diol was obtained almost exclusively. It is clear that the former reduction gave kinetically-controlled products and that the latter gave thermodynamically-stable products. Unusual results were obtained by changing the hydrolysis conditions for the lithium aluminium hydride reduction products and these are explained assuming that the intermediate aluminium alkoxide is oxidized by acid.
Reactions of a Variety of Diazoalkanes with o-Sulfobenzoic Anhydride
Authors: Oshima Takumi , Nagai Toshikazu 
Published: July 2006

Abstract
It was found that a number of diazoalkanes (I) bearing a relatively small substituent reacted with o-sulfobenzoic anhydride (II) in acetonitrile at an ordinary temperature to give the o-(substituted glycoloyl)benzenesulfonic acid sultones (IV), which correspond formally to the products from the insertion into the C–O bond of II by the carbenes, while diaryldiazomethanes underwent decomposition under the same conditions to produce the corresponding tetraarylethylenes (V) instead of the inserted products (IV). The olefin formation reaction was very fast compared to the sultone formation and was considered to be the result of the acid-catalyzed decomposition caused by the contaminant o-sulfobenzoic acid (III) which was derived from II. The kinetics and the mechanism of these reactions were discussed on the basis of the nature of diazoalkanes.
Fundamental Studies on the Ion-Exchange Separation of Boron Isotopes
Authors: Kakihana Hidetake , Kotaka Masahiro , Satoh Shohei , Nomura Masao , Okamoto Makoto 
Published: July 2006

Abstract
The single-stage separation factors for boron isotopes between an ion-exchange resin and an external solution were determined, using an ion-exchange breakthrough operation. The lighter isotope boron-10 was considerably enriched in the anion-exchange resin phase. The separation factor was very much influenced by the boric acid concentration in the external solution, but not as much influenced by the kind of the anion exchange resin used and operation temperature. The separation factor increased with a decrease in the boric acid concentration of external solution from 1.008 (0.501 mol/l) to 1.016 (0.010 mol/l). The value of the separation factors obtained experimentally were compared with those estimated on the basis of the theory of the two-phase distribution of isotopes.
A Practical Synthesis of Polyhalomethyllithium-Carbonyl Adducts
Authors: Taguchi Hiroaki , Yamamoto Hisashi , Nozaki Hitosi 
Published: July 2006

Abstract
The title adducts are produced upon treatment of a mixture of polyhalomethane and a carbonyl compound with a hindered lithium amide. The kinetically controlled, selective lithiation of the halide enables us to avoid a troublesome procedure involving preformed lithium carbenoid. The halide components examined are dichloromethane, dibromomethane, diiodomethane, chloroform, and bromoform, while the carbonyl ones are ubiquitous ketones and nonanal. A gem-dichloroallyllithium is generated similarly from 3,3-dichloropropene and, furthermore, the procedure is successfully extended to the Darzens-type reaction of α-halo esters.
Carbon-13 NMR Spectra of π-Allyl Palladium Chloride Complexes
Authors: Senda Yasuhisa , Suda Hiroshi , Ishiyama Jun-ichi , Imaizumi Shin , Kasahara Akira , Izumi Taeko , Kato Takao 
Published: July 2006

Abstract
The 13C NMR spectra of thirteen acyclic and cyclohexenyl π-allyl palladium chloride dimers are examined and their chemical shifts are compared with those of the corresponding olefins. The signals for the central carbons of the π-allyl palladium moiety were displaced upfield by 8.0–25.5 ppm and those for the terminal carbons by 34.9–55.9 ppm compared to the corresponding carbons of the corresponding olefins.
Accordionlike Skeletal Motions of CH3NHCONH(CH2)nCH3 (n=1–15)
Authors: Mido Yoshiyuki , Fujita Fumiko , Kitagawa Teizo 
Published: July 2006

Abstract
Solid CH3NHCONH(CH2)nCH3 (n=1–15) gave two intense Raman lines in the 100–500 cm−1 region. The frequency of one of them varied with n, but that of the other was unvarying. The n-dependent frequencies fit the theoretical ν-δ curve of C–C–C deformation of polyethylene and were, therefore, assigned to the accordion modes.
The Channeling of Hot H Atoms in the Radiolysis and Photolysis of Crystalline Alkane
Authors: Miyazaki Tetsuo 
Published: July 2006

Abstract
The possibility of a long migration of hot H atoms through crystalline alkane is discussed in terms of a simple channeling theory. The potential energy surface for an H atom in crystalline neopentane shows that the channeling directions are perpendicular to the [110] and [100] planes. The energy dependence of the channeling of hot H atoms is discussed.
The Coercive Force of γ-Fe2O3 Prepared from γ-FeOOH
Authors: Hamada Shuichi , Kuma Kenshi 
Published: July 2006

Abstract
The γ-Fe2O3 with a high coercive force was prepared by reducing the acicular γ-FeOOH at 300 °C and by then reoxidizing it at 250 °C. A conversion from γ-FeOOH to γ-Fe2O3 at lower temperatures was effective in obtaining acicular particles without pores because of the large mobilities of ions in the crystal.
Preparation and the Acid Hydrolysis of N-(2-Hydroxyethyl)ethylenediamine-N,N′,N′-triacetate Complex of Di-μ-oxo-bis(oxomolybdenum(V))
Authors: Sasaki Yoichi , Morita Tomoji S 
Published: July 2006

Abstract
A hedta (H3hedta=N-(2-hydroxyethyl)-ethylenediamine-N,N′,N′-triacetic acid) complex of molybdenum(V), Mo2O4(hedta)(H2O)−, has been prepared and characterized. The rate of acid hydrolysis of this complex in an aqueous perchloric acid solution ([H+]=0.5–2.0 mol dm−3; I=2.0) is of similar magnitude to that of Mo2O4(edta)2−(H4edta=ethylenediaminetetraacetic acid), increasing with increase in [H+].
The Conformations of Nickel(II) Complexes with edda-Type Optically Active Polyamino Carboxylic Acids in Aqueous Solutions
Authors: Murakami Tasuku , Hirako Ichiro , Hatano Masahiro 
Published: July 2006

Abstract
Circular dichroism (CD) and proton magnetic resonance (PMR) spectra of nickel(II) complexes containing a series of ethylenediamine-N,N′-diacetic acid (H2edda)-type optically active quadridentate ligands were measured in aqueous solutions. The epro complex which is an edda-type optically active ligand containing l-proline residues is found to exhibit the same CD spectrum as complexes of other edda-type ligands containing l-alanine, l-valine, l-phenylalanine, and l-serine residues. The CD and PMR spectra of the mixed complexes of these edda-type ligands having an oxalate ion was also measured. From the CD and PMR spectral data, it is concluded that these complexes stereospecifically take the Δ-s-cis form in solution. The large contact shift observed for the a protons of the amino acidate moieties indicates that the substituent groups become axial to the chelate plane.
A New Synthetic Approach to Esters of β-Keto Thiocarboxylic SAcids
Authors: Wakui Toshimitsu , Yamaguchi Haruzo , Motoki Shinichi 
Published: July 2006

Abstract
Esters of β-keto thiocarboxylic S-acids (5) were synthesized from S-ethyl bromothioacetate (1), through a reaction sequence involving the reduction of sulfonium ylides (4) with zinc in acetic acid.
Tungsten Hexachloride-catalyzed Decomposition of Diazo Compounds. A Novel Oxazole Synthesis
Authors: Kitatani Katuzi , Hiyama Tamejiro , Nozaki Hitosi 
Published: July 2006

Abstract
Benzoylphenyldiazomethane and diazoacetophenone react with several nitriles in the presence of WCl6 catalyst to produce 2-substituted 4,5-diphenyloxazoles (1a–d) and 2-methyl-5-phenyloxazole (2) in good yields. The remarkable catalysis is ascribed to the good affinity of tungsten with carbenes. The catalytic decomposition of diphenyldiazomethane yields diphenylcarbenium ion, which is transformed into triarylmethanes in aromatic solvents.
Synthesis of 2-Alkoxy-3,4,6-trihydroxyacetophenones
Authors: Hatakeda Kiyotaka , Saito Norio , Ito Shota , Asano Takashi 
Published: July 2006

Abstract
2-Alkoxy-3,4,6-trihydroxyacetophenones have been prepared from 2,3,4,6-tetrakis(benzyloxy)acetophenone (II) in good yields by the following reactions: hydrolysis of II to 2-hydroxy-3,4,6-tris(benzyloxy)acetophenone (IIIa), alkylation of IIIa to 2-isopropoxy and 2-ethoxy-3,4,6-tris(benzyloxy)acetophenones (IVa and VIb), and hydrogenolysis of IVa and IVb to the corresponding 2-alkoxy-3,4,6-trihydroxyacetophenones (Va and Vb).