bluuebunny/crossref_metadata_2025 huggingface dataset:
Ligand-Ligand Interaction in [Zn(1,10-phenanthroline)2(H2O)2](NO3)2 and [Zn(2,2′-bipyridyl)3](NO3)2
Authors: Ohno Takeshi , Kato Shunji
Published: July 2006

The interaction between ligands in the excited state and in the ground state was examined by exploring the photophysical behaviors of ligands in the bis- and the tris-bidentate complexes. Although no exciton splitting was observed in the absorption spectra of [Zn(bipy)3](NO3)2 and [Zn(phen)2(H2O)2](NO3)2 at 77 K, the fluoresccence yields of both complexes increased in comparison with those of the corresponding mono-bidentate complexes. It is probable that this change is caused by a delocalization of the excited singlet state, because a variation in Franck-Condon factors and a depolarization of the fluorescence accompanied it. In addition to the ligand-ligand interaction 1,10-phenanthroline and 2,2′-bipyridyl suffered from coordination effects. They have larger fluorescence yields and smaller phosphorescence yields than the free molecules. The decrease on the transition rate of the intersystem crossing is probably due to the changes in the energy levels of 1(n-π*) and 3(n-π*), caused by the metal-ligand bond using a “non-bonding” orbital in the free ligands.
Vibrational Assignments and Rotational Isomerism of Dichloroethylmethylsilane and 2,2-Dichlorobutane
Authors: Ohno Keiichi , Shiro Yuji , Murata Hiromu
Published: July 2006

The vibrational spectra of dichloroethylmethylsilane and 2,2-dichlorobutane have been measured. The vibrational assignments of these molecules have been made in relation to the rotational isomerism. The normal vibration calculations based on the modified Urey-Bradley force field have been carried out and have confirmed for both molecules that, in the liquid state, the trans and gauche isomers coexist, while the trans isomer alone persists in the crystalline state.
The Crystal Structure of Dichlorobis(acetoxime)palladium
Authors: Kitano Yukishige , Kobori Kiyotomi , Tanimura Masamitsu , Kinoshita Yukio
Published: July 2006

The crystal structure of dichlorobis(acetoxime)palladium, PdCl2(C3H6NOH)2, has been determined from three-dimensional single-crystal X-ray photographic data. The crystals belong to the monoclinic system (space group P21/a), with two formula units in a cell with dimensions: a=8.709±0.007, b=13.996±0.005, c=4.756±0.006 Å, and β=95.60±0.05°. The structure was established by the heavy-atom method and was refined by the block-diagonal least-squares procedure. The Pd atoms are spaced at intervals of 4.76 Å along the c-axis and have a trans planar coordination, with two Cl atoms at 2.30 Å and two N atoms of the oxime groups at 2.03 Å. The oxime plane is twisted about the Pd–N bond by 72.7° from the coordination plane defined by the Pd, Cl, and N atoms. The complex molecules are hydrogen-bonded with each other in strings of an indefinite length along the c-axis, and the hydrogen-bond distance between the O atom of the oxime and the Cl atom is 3.07 Å.
The Effect of Organic Additives on the Micelle Formation of Dodecylammonium Halides in Aqueous Solutions
Authors: Miyagishi Shigeyoshi
Published: July 2006

The critical micelle concentration (CMC) of dodecyl ammonium halides and the degree of dissociation of the micelle (α) of dodecylammonium chloride were determined as functions of the concentrations of the organic additives by measuring the conductivity and the emf of the following cell: calomel/1 M-KCl/sample solution/AgCl, Ag. The CMC was raised more in the presence of acetone and dioxane than in that of acetamide, formamide, urea, and methanol, and was diminished by adding alcohols (C2–C4). The effect of the alcohols on CMC decreased in the order of the diminished hydration of the counterion, acetone and dioxane were considered to affect the dodecylammonium iodide solution specifically. The dissociation of the micelle was enhanced in the presence of organic additives. Further, we estimated the solubilized amount of the additives from the degree of dissociation of the micelle and attempted to make quantitative estimation of the increment of CMC produced by organic additives.
The Thermal Reaction of Hydrogen and Nitric Oxide
Authors: Tadasa Kohji , Imai Naomi , Inaba Tetsuo
Published: July 2006

The kinetics of the H2–NO pyrolysis was studied at 400°C; the reaction was found to be first-order in H2 and to be independent of NO. It is suggested that the reaction proceeds by means of a free-radical chain mechanism: H2+NO(surface)→HNO+H(1), H+NO\ightleftharpoonsHNO (2), 2HNO→2OH+N2 (3) OH+H2→H2O+H(4) and 2HNO→H2O+N2O(5). This reaction scheme resembles that proposed for the CH2O–NO pyrolysis at 500°C except for the initiating step (1), which takes place on the wall of the vessel in the H2–NO pyrolysis.
Interaction between Water and Hydroxylated Surface of Silica-Alumina
Authors: Morimoto Tetsuo , Nagao Mahiko , Imai Junichiro
Published: July 2006

The interaction between water and the fully-hydroxylated surfaces of silica,alumina and silica-alumina has been investigated by measuring the physisorption isotherms of water at three temperatures and by computing the isosteric heat of adsorption and the site energy distribution therefrom. The number of adsorption site evaluated on the surfaces of each of the two component oxides decreases exponentially with the increase in the site energy, whereas that of the silica-alumina samples gives a peak at a relatively high energy region, suggesting the presence of strong water-physisorption sites characteristic to silica-alumina. These results can be elucidated on the basis exponentially of the postulation that new sites having protonic acid character appear when the two component oxides contact with each other, as described previously. Furthermore, it is found that the strength of such new sites for physisorption of water increases with decreasing content of alumina in silica-alumina.
Phase Transition of Solid Hexabromoethane
Authors: Koide Tsutomu , Tsujino Masami , Sawada Kazuhiro , Oda Tsutomu
Published: July 2006

The phase transition point of solid hexabromoethane was found at 177°C, above which the crystal is a body centered cubic lattice with two molecules in a unit cell, having a cell length of 7.80 Å at 185°C. From an analysis of entropy change, it seems that random orientations of the molecular axis would occur at the transition point. The influence of halogen substitution is discussed. It was concluded that the phase transition will be dominated mainly by the geometrical properties of the molecules.
Apparent Dipole Moments and Dielectric Relaxation Times of 1,4-Benzoquinone and Its Derivatives in Solutions
Authors: Nagai Tohru , Takahashi Hiroaki , Higasi Keniti , Sutton Leslie E , Waddington David
Published: July 2006

Atom polarisations, apparent dipole moments and dielectric relaxation times of 1,4-benzoquinone in various solvents were determined together with those of some of its derivatives in benzene solution. Solvent effects on the apparent dipole moments of 1,4-benzoquinone and its derivatives were examined in comparison with the absorption spectra in the submillimetre region.
Transition-metal Complexes of Pyrrole Pigments. XI. Zinc(II) Chelates of Some Dipyrromethenes
Authors: Murakami Yukito , Sakata Kazunori
Published: July 2006

The zinc (II) chelates of five dipyrromethenes which have methyl substituents to a various extent, as well as that of 5,5′-diphenyldipyrromethene, have been prepared. The behaviors of methyl resonances upon metalcoordination were classified into three cases: (1) a down-field shift, but not greater than that of the corresponding ligand hydrochloride (3,3′-CH3); (2) nearly no change in chemical shift (4,4′-CH3); and (3) a profound up-field shift, the methyl resonance of the corresponding ligand hydrochloride showing a down-field shift on the contrary (5,5′-CH3). A marked change in chemical shift for the methine proton upon zinc(II)-coordination is related to conjugation in the chelate ring–the presence of aromaticity. As a whole, methyl resonances for the zinc chelates are consistent with the tetrahedral coordination geometry. Electronic absorption peaks for the zinc chelates, which were located in the lowest energy region with the highest intensity, were assigned to the intra-ligand π→π* transition and the metal→ligand charge-transfer as well. Vibrational absorption bands appearing in the 1600 cm−1 range and in the 400–350 cm−1 region have been assigned to the skeletal stretching mode of the dipyrromethene moiety and the metal-ligand stretching mode, respectively, for the zinc chelates.
Studies of the Substituent Effect on the Stability Constants of Bis(2-hydroxy-4 or 5-substituted acetophenonato)copper(II)
Authors: Haruta Masami , Yoshida Zen-ichi , Ogoshi Hisanobu
Published: July 2006

The dissociation constants of eleven 2-hydroxy-4 or 5-substituted acetophenones were determined in a 22.5% water–dioxane-mixed solvent system at 25 and 40°C by potentiometric titration. They were then discussed in terms of the electronic effect of the substituents and the linear-free-energy relationship. The stability constants bis(2-hydroxy-4 or 5-substituted acetophenonato)copper(II) were also determined under the same experimental conditions; a linear relationship between the dissociation constants and the stability constants was obtained for bis(2-hydroxy-4 or 5-substituted acetophenonato)copper(II). No significant difference has been found in the effects of 4- and 5-substituted groups on the stability constants.
ESR and Optical Absorption Studies of Various Bis(N-salicylidenealkylaminato)copper(II) Complexes with Tetrahedrallydistorted Coordination Geometry
Authors: Yokoi Hiroshi
Published: July 2006

The ESR and visible absorption spectra of a number of bis(N-salicylidenealkylaminato)copper(II) complexes with different kinds of alkyl groups were measured in toluene. The coordinations of these complexes in toluene are distorted towards a tetrahedral geometry to varying extents; the relationship between the degree of the distortion and the ESR and visible absorption parameters was systematically investigated. Especially, the experimental fact that the absolute values of the hyperfine coupling constant with the copper nucleus decrease with an increase in the degree of distortion was discussed. A configurational equilibrium between two species with different degrees of the distortion was found to exist for the complexes with R=isopropyl and cyclohexyl in toluene.
The Gas-chromatographic Behavior of Perhaloalkanes
Authors: Iwata Ren , Makide Yoshihiro , Tominaga Takeshi
Published: July 2006

The retention indices of perhaloalkanes (perbromochlorofluoroalkanes, etc.) were measured by using a gas chromatograph with a squalane, Silicone DC 550, or Methoxy polyethylene glycol 350 column, and the correlation of the retention index with various physicochemical parameters was investigated. The retention index was found to correlate linearly with the composition of the halogen atoms in the perhaloalkane molecules; the correlation diagram appears to be of special analytical importance. The relationship between the retention index and the boiling point was also studied. The retention index was correlated linearly with the molar refractivity of the perhaloalkanes, irrespective of the polarity of the columns. The molar refractivity appears to be the inherent parameter which is most adequate for considering the regularity of the retention index. The effect of the polarity of the stationary phase on the retention index was also investigated.
Synthesis of Dimeric and Trimeric 2-(p-Tolyloxy)ethyl Acetate-Formaldehyde Polymer Model Compounds
Authors: Ninagawa Akira , Matsuda Haruo , Matsuda Sumio
Published: July 2006

The dimeric and trimeric 2-(p-tolyloxy)ethyl acetateformaldehyde polymer model compounds and the halogenated compound of the dimer were synthesized. 2,2′-Methylenebis(5-methyl-1,2-phenyleneoxy)diethyl acetate was synthesized by the reaction of 2-(p-tolyloxy)ethyl acetate with formaldehyde in acidic media. 2-[2-(2-Acetoxyethoxy-3-chloro-5-methylbenzyl)-4-methylphenoxy]ethyl acetate was prepared by the reaction of 6-chloro-4,4′-dimethyl-2,2′-methylenediphenol with 2-chloroethanol, followed by treatment with acetic anhydride, and 2-[2,6-bis(2-acetoxyethoxy-5-methylbenzyl)-4-methylphenoxy]ethyl acetate from 2,6-bis(2-hydroxy-5-methylbenzyl)-4-methylphenol.
Dopaquinone and Related Compounds. The Reaction with Cyclopentadiene
Authors: Omote Yoshimori , Komatsu Toshihiko
Published: July 2006

The trapping of o-quinones produced during the oxidation of 4-substituted catechols(I, R=CH3, CH2CH2CO2H, CH2CH2NH3Br, CH2CH(NH3Cl)CO2CH3) in the presence of cyclopentadiene affords adducts, which are changed into 8-substituted 5,6-diacetoxy-1,4-dihydro-1,4-methanonaphthak nes(IV, R=CH3, CH2CH2CO2H, CH2CH2NHCOCH3, CH2CH(NHCOCH3)COCH3) by treatment with acetic anhydr de-pyridine Dopaquinone (IIe) is trapped with cyclopentadiene, followed by acetylation and methylation with acetic anhydride–pyridine–methanol (13 : 2 : 2) to give the N-acetyl-2-(5,6-diacetoxy-1,4-dihydro-1,4-methanonaph-thyl-8)-l-alanine methyl ester (IVd).
Reactions of Group IV Organometallic Compounds. XXX. Stepwise Addition of Isocyanates and Isothiocyanates with N-Trimethylstannyl(diphenylmethylene)amine
Authors: Suzuki Hiroharu , Itoh Kenji , Matsuda Isamu , Ishii Yoshio
Published: July 2006

Stepwise addition of two isocyanates to N-trimethylstannyl(diphenylmethylene)amine, Ph2C=NSnMe3, gives 3,4-dihydro-1,3-dialkyl-4,4-diphenyl-6-trimethylstannoxy-1,3,5-triazin-2(1H)-one (II) by a polar [4+2] cycloaddition of the 1/1 adduct and the second isocyanate. The isothiocyanate adducts of Ph2C=NSnMe3 react with either isocyanates or isothiocyanates to yield the corresponding consecutive insertion products (IV).
Synthesis of Butirosin B and Its 3′,4′-Dideoxy Derivative
Authors: Ikeda Daishiro , Tsuchiya Tsutomu , Umezawa Sumio , Umezawa Hamao
Published: July 2006

The total synthesis of butirosin B (5) is described. Its 3′,4′-dideoxy derivative (11) has been synthesized, a cyclic carbamate derivative (2) being used as the key compound. The dideoxy derivative (11) was prepared by hydrogenation of a 3′,4′-unsaturated derivative (10) obtained by the reaction of a di-O-mesyl derivative (9) with sodium iodide and zinc dust. The dideoxy derivative (11) was found to have significant activity against resistant bacteria producing phosphotransferase I.
Reactions of Ethylene with Chloroform Initiated by Amine–Ferrous Chloride System
Authors: Asahara Teruzo , Sen\={o} Manabu , Ohtani Noritaka
Published: July 2006

The reactions of ethylene with chloroform initiated by alkylamine-ferrous chloride systems were examined in detail. Two main products, α,α,α-trichloroalkanes (I) and α,α,ω-trichloroalkanes (II), were obtained. Their composition was independent of the kind of amine but dependent upon the total carbon number of alkylamine. When amines having higher alkyl groups were used, the main product was α,α,ω-trichloropropane (II-1). When lower alkylamines were used, the main products were α,α,α-trichloroalkanes which contained considerable amounts of higher telomers. The results support the view that the reactions proceed according to the “caged free radical” process.
Thiocarbonyl Ylides. Attempted Preparation and Related Reactions
Authors: Mitamura Shuichi , Takaku Masaaki , Nozaki Hitosi
Published: July 2006

The attempted preparation of thiocarbonyl ylides (I) by the proton abstraction of thiouronium salts (III) has disclosed a fast isomerization of I to enethiols (V) (Y=H) and an alternative desulfurization to enediamines (VII) (Y=Ph), the by-products being olefins (VIII) and sulfides (IX). The second route to I examined consists of the reaction of tetramethylthiourea (II) with diazomalonate, which gives rise to enediamine (VIIg). Rotation about the C=C bond of enediamines is discussed on the basis of IR and NMR spectra.
ESR Study on Molecular Motion of CO2− Radical Adsorbed on Zeolite
Authors: Edlund Ove , Sohma Junkichi , Sogabe Kunihisa
Published: July 2006

Molecular motion of 13CO2− radical adsorbed on zeolite was quantitatively analysed from the temperature variation of the separation of hyperfine structure of ESR spectra from 13CO2− radicals.
Ionic Equilibria in Micellar Solutions
Authors: Shirahama Keishiro
Published: July 2006

Ionic equilibria in micellar solutions are discussed on the basis of micelle-monomer equilibrium, massconservation, and electroneutrality. The present treatment gives a larger degree of counterion dissociation from micelles than ever estimated. Another conclusion is a decreasing concentration of monomeric surface-active ion as micellar concentration increases.
Dissociative Electron Attachment to (Chloroethyl)benzenes in γ-Irradiated Organic Glassy Matrices
Authors: Saito Takayuki , Yoshida Hiroshi
Published: July 2006

Free radicals formed from (1- and 2-chloroethyl) benzene in γ-irradiated organic matrices were studied with a fluroescence spectrophotometer. The observed spectra suggest the transformation of phenetyl radical primarily formed from (2-chloroethyl)benzene to α-methyl-benzyl radical and indicate interaction between the α-methylbenzyl radical, formed from both (1- and 2-chloroethyl)benzene, and chloride anion before complete dissociation.
Formation of Erbium and Holmium Mixed Completes with Complexane and Carbonate Ion
Authors: Taketatsu Tomitsugu
Published: July 2006

The formation of erbium and holmium mixed complexes with one species of complexanes and carbonate ion in alkaline solution (pH 10.5–10.7) was investigated spectrophotometrically. The results suggest that carbonate ion additionally combines with the EDTA and CyDTA chelates, while does not with the DTPA chelates.
Olefin Disproportionation by Molybdenum(0) Complexes and Aluminum Halides
Authors: Hidai Masanobu , Tatsumi Takashi , Uchida Yasuzo
Published: July 2006

MoN2(PPh3)2·PhMe and Mo(CO)(PPh3)2 were activated by aluminum halides to give catalysts effective for the disproportionation of 2-pentene.
The Photochemical and the Thermal Reaction of Dimethyl trans-Spiro[2.6]nona-4,6,8-triene-1,2-dicarboxylate
Authors: Saito Katsuhiro , Toda Takashi , Mukai Toshio
Published: July 2006

The irradiation of dimethyl trans-spiro[2.6]nona-4,6,8-trien-1,2-dicarboxylate (I) with a low-pressure mercury lamp afforded two tricyclic valence isomers (II and III). Upon heating, II and III were converted into dimethyl trans-indan-1,2-dicarboxylate (IV), which was also obtained by the thermolysis of I. In order to elucidate the reaction mechanism for the formation of IV from I, we studied the thermal reaction using a deuteriumlabelled compound (V).
4-Oxo-1,2,3,4-tetrahydroquinazolines, V. Ring Expansion Reaction of 1-Methyl-3-phenyl-4-oxo-3,4-dihydroquinazolinium Bromide with Diazoalkanes
Authors: Yamada Yoshihisa , Oine Toyonari , Inoue Ichizo
Published: July 2006

Reactions of 1-methyl-3-phenyl-4-oxo-3,4-dihydroquinazolinium bromide (13) with diazoalkanes were investigated. Treatment of 13 with diazomethane in EtOH gave a ring-expansion product 14 in a good yield. A mechanism which involves the formation of azirinoquinazolinium bromide and a subsequent SN1 type ring opening was discussed. Treatment of 13 with phenyldiazomethane also afforded benzodiazepine 16. However, reaction of 13 with ethyldiazoacetate in the presence of CuSO4 gave 4-oxo-1,2,3,4-tetrahydroquinazoline 17.
A Molecular Orbital Study on the Effects of Excess Charges at the Donor and Acceptor Atoms on the Hydrogen Bond
Authors: Igawa Akira , Fukutome Hideo
Published: July 2006

Effects of the excess charges at the donor and acceptor atoms on the properties of the hydrogen bond were studied in a simple three-center four-electron model for a hydrogen bond system using CNDO/2 type molecular orbital calculation. It was shown that three types of hydrogen bonds, normal, proton transferred and abnormal, are possible according to the value of the excess charges. The dependence of the hydrogen bond distance, proton equilibrium distance, frequency of proton stretching vibration and hydrogen bond energy on the excess charges were calculated for the normal type hydrogen bond. The correlations between these quantities obtained by changing the amounts of the excess charges are in good agreement with the experimental results, suggesting that the excess charges at the donor and acceptor atoms primarily determine the correlation. The potential of proton movement at the equilibrium hydrogen bond distance is shown not to have double minima for any value of the excess charges, indicating that the excess charges are not essential for producing a double well potential.
The INDO and CNDO/2 SCF LCAO MO Calculation of Intermodular Forces and Their Pairwise Additivity
Authors: Hashimoto Masao , Isobe Taro
Published: July 2006

The assumption of pairwise additivity of the intermolecular forces was examined within a CNDO/2-Clementi approximation. It was found that the deviation from the pairwise additivity, defined as the difference between the three-body interaction and the sum of the two-body interaction energies in the system of three neighboring molecules in a crystal, was small enough to be neglected as compared with the lattice energy. The CNDO/2 -Glementi method, in which the overlap integrals are calculated by using the Clementi AO’s, was found to be more useful than the usual CNDO/2 method, in which the overlap integrals are calculated by means of Slater AO’s. The discrepancy in the calculated interaction energies from the experimental ones in the form of the heat of sublimation was found to be quite large for CO. This discrepancy becomes small, though, if the centers of the molecules are displaced away from the origin and along the nonintersecting threefold axes of the unit cell; the crystal structure belongs not to the Pa3 space group, but to the P213 space group. From a comparison of the CNDO/2-Clementi results and the results of the exp-6 potential superimposed on the quadrupole-quadrupole interaction potential, it was found that the former is superior to the latter in anticipating the conformation of the (CO2)2 dimer.
Theory of Ion Cyclotron Resonance Power Absorption for Nonreactive and Reactive Ions
Authors: Aoyagi Katsuyuki
Published: July 2006

An exact solution of the equation of motion and exact expressions of the ion current in ion cyclotron resonance power absorption were obtained. Instantaneous and total power absorptions together with power absorption line shapes were derived. Ion current expressions were also derived for both nonreactive and reactive ions over the whole range of pressure. The results agreed with those obtained previously for high and low pressures with appropriate approximation. The rate constants for the disappearance of primary ions and for the formation of nonreactive secondary ions were obtained from the ion cyclotron resonance experiments. The results showed good agreement with those obtained by other methods.
The Crystal Structure of dl-1,1,4aα-Trimethyl-2α-hydroxy-8β-methoxy-1,2,3,4,4a,5,6,7,8,9-decahydrophenanthrene
Authors: Furusaki Akio , Hamanaka Nobuyuki , Matsumoto Takeshi
Published: July 2006

The crystal structure of the title compound has been determined from three-dimensional data collected on an automatic, four-circle diffractometer. The racemic crystals are triclinic, with two molecules in a unit cell of these dimensions; a=10.502, b=11.706, c=7.488 Å, α=71°33′, β=91°46′, and γ=116°22′. The space group is P\bar1. The structure was solved by the symbolic addition method and was then refined by the block-diagonalmatrix least-squares method, with isotropic temperature factors for the hydrogen atoms and with anisotropic ones for the others. The final R value was 6.7%. The length of the C–C single bond opposite to the double bond in the cyclohexene ring is only 1.34±0.01 Å. This apparent remarkable shortening can be well explained on the assumption that the two atoms concerned vibrate vigorously with parallel and antiparallel harmonic components perpendicular to the plane of the ring. It is shown that, if the root-mean-square amplitudes of the former components are taken to be equal to that of the thermal vibration of the carbon atom adjacent to one of the two atoms, the above C–C distance, corrected for these antiparallel motions, becomes quite reasonable: 1.60 Å.
An Investigation of the Gas-Solid Interface Reaction on the Surface of Ag and Ag2S
Authors: Katsumoto Masayuki , Fueki Kazuo , Mukaibo Takashi
Published: July 2006

In order to elucidate the mechanism of the redox reaction at the gas-solid interface, the isotopic exchange between H2S and D2 on Ag and Ag2S has been studied in the temperature range from 410 to 521°C. The transfer of isotopic species between “hydrogen sulfide” 1) and “hydrogen” 1) was found to proceed by means of the reaction:

“H_2S”^1)\oversetk_i\undersetk_i’\ightleftarrows“H_2”^1)+S(ad)

on both surfaces. From the analysis of the kinetic data, the redox reaction rate constants, ki and ki′, were determined as a function of the sulfur activity. It was found that ki is inversely proportional to the sulfur activity, whereas ki′ is independent of it. The mechanism of the reaction on the surfaces of Ag and Ag2S is discussed.
An ESR Study of Nitric Oxide Adsorbed on Silica Gel
Authors: Iwaizumi Masamoto , Kubota Shozo , Isobe Taro
Published: July 2006

Nitric oxide adsorbed on silica gel was investigated by ESR. It was found that there are at least two adsorption sites for nitric oxide; one of them is on the silica gel which has been pretreated at low temperatures (below ca. 500 °C) (Site L), while the other is predominantly on the silica gel which has been pretreated at high temperatures (above ca, 500 °C) (Site H). The crystal-field splitting of the Πx* and ΠY* states, which are originally degenerate, was determined to be 0.26 eV for the nitric oxide adsorbed on Site L and 0.52 eV for the nitric oxide on Site H. The temperature dependence of the ESR spectrum was also examined, and the average crystal field acting on nitric oxide was found to decrease with an increase in the temperature.
Molecular Structure of N-Methylformamide as Studied by Gas Electron Diffraction
Authors: Kitano Mitsuo , Kuchitsu Kozo
Published: July 2006

The bond distances (rg) and angles (ra) in N-methylformamide HCONHCH3 have been determined by gas electron diffraction as follows: N–C (methyl)=1.459±0.006 Å, C(carbonyl)–N=1.366±0.008 Å, C=O=1.219±0.005 Å, C–H(methyl)=1.114±0.025 Å, <N–C=O=124.6±0.5° and <C–N–C=121.4±0.9°, where uncertainties represent estimated limits of experimental error. Systematic trends are observed among the skeletal structures of formamide, acetamide, N-methylformamide and N-methylacetamide. A conformer with the C(carbonyl)–H and N–C(methyl) bonds trans to each other is found to be dominant in the gas phase. The presence of a small fraction of the cis conformer is suggested, but the experimental evidence is not conclusive.
The Chemistry of Americium. II. The Behavior of Am(III), Am(V), and Am(VI) in Column Chromatography, with Bis(2-ethylhexyl)phosphoric Acid Used as the Extractant
Authors: Hara Mitsuo , Suzuki Shin
Published: July 2006

The behavior of Am(III), Am(V), and Am(VI) in column chromatography with bis(2-ethylhexyl)phosphoric acid(HDEHP) used as the extractant were investigated in comparison with that of Np(IV), Np(V), and Np(VI). When the solution of Am(VI) was submitted to the column chromatography, it was found that Am(VI) was rapidly reduced to Am(V) and partially to Am(III) by HDEHP, irrespective of the conditions, such as the flow rate, the acidity, and the composition and temperature of the influent. The optimum conditions for the separation of Am(V) and Am(III) and for the preparation of the Am(V) solution were established by utilizing the difference in the adsorbability on the column bed between Am(III) and Am(V). When a freshly-prepared Am(V) solution was submitted to column chromatography, it was found that Am(V) was also reduced to Am(III) as well as Am(VI) by HDEHP. The percentage of the Am(V) fraction eluted strongly depended on the conditions in the column chromatography, but it was found to be constant within the limits of experimental error under definite conditions as long as the same column was used. This fact was applied to the determination of the Am(V) content in the mixed solution of Am(III) and Am(V). The content of Am(V) decreased slowly in the nitrate, acetate, sulfate, and perchlorate solutions at lower temperatures, but it rapidly decreased in the chloride, iodide, sulfite, and hydrogen peroxide solutions even at 0 °C. The content of Am(V) decreased more rapidly at higher temperatures, and the kinetic analysis showed that the reduction of Am(V) apparently followed the first-order kinetics in the acetate solutions.
Syntheses of N,N′-Bis(1-acetonylethylidene)ethylenediamine Complexes of Rare Earth Perchlorates
Authors: Yoshida Norifumi , Matsumoto Akira , Shiokawa Jiro
Published: July 2006

N,N′-Bis(1-acetonylethylidene)ethylenediamine(AEH2) complexes were prepared by the reaction of hydrous rare earth perchlorates with AEH2 in methanol. Elemental analysis, X-ray powder diffraction analysis, pH titration, IR and luminescence spectrometries indicated that the complexes of the lighter rare earths were Ln(AEH2)4(ClO4)3, where Ln are La, Pr, Nd, and Sm, while the complexes of the heavier rare earths were hydroxocomplexes, Ln(AEH2)2(ClO4)2(OH)·H2O, where Ln are Gd, Dy, and Er. Anhydrous gadolinium perchlorate was reacted with AEH2 in methanol under anhydrous conditions to give Gd(AEH2)4(ClO4)3. It was possible that a water molecule played an important role in the complexation of rare earth perchlorates with AEH2 in methanol. The formation of the hydroxocomplexes with AEH2 was related to the low coordinating ability of the perchlorate ion and to the charge densities of the rare earth ions as well as to the basicity of AEH2.
Thermal Reaction in a Series of Ammineisothiocyanatochromium(III) Complexes in Solid State
Authors: Oki Hisaya , Yasuoka Meiji , Tsuchiya Ryokichi
Published: July 2006

The thermal decomposition of [Cr(NH3)6](SCN)3, [Cr(NCS)(NH3)5](SCN)2 and cis-[Cr(NCS)2(NH3)4]SCN in solid state was studied by isothermal as well as continuous temperature-rise methods. Under isothermal heating at 140°C, [Cr(NH3)6](SCN)3 changed stepwise to cis, trans-[Cr(NCS)3(NH3)3] through trans-[Cr(NCS)2(NH3)4]SCN, [Cr(NCS)(NH3)5](SCN)2 turning to the cis-trans complex over the trans complex in the same manner as [Cr(NH3)6](SCN)3. Under the continuous temperature-rise, [Cr(NH3)6](SCN)3, [Cr(NCS)(NH3)5](SCN)2 as well as trans-[Cr(NCS)2(NH3)4]SCN were found to be directly converted into cis,trans-[Cr(NCS)3(NH3)3].
Derivatographic Studies on Transition Metal Complexes. XIII. Thermal Decomposition of [Ni(N2H4)6]X2 Complexes
Authors: Tsuchiya Ryokichi , Yonemura Masaaki , Uehara Akira , Kyuno Eishin
Published: July 2006

The thermal decomposition of [Ni(N2H4)6]X2 (X=Cl, Br, I) in solid phase was investigated by means of derivatography and IR spectral measurement. It was found from the derivatography that the decomposition of the chloride and bromide proceeded via tris-, bis-, and mono-hydrazine complexes as metastable reaction intermediates, while tetra-hydrazine complex was produced in the decomposition of the iodide instead of the tris-one which appeared in the chloride and bromide. IR spectra showed that, although the hexa-hydrazine complex as a starting material contains only unidentate hydrazine coordinated by either one of terminal nitrogen atoms, all the reaction intermediates have bidentate one bridging between two nickel ions. In particular, it was of much interest that the decomposition of these hydrazine complexes was remarkably exothermic, a part of the reasons being discussed.
Photo-Beckmann Rearrangements of Oximes of Androsterone and 13α-Androsterone
Authors: Suginome Hiroshi , Uchida Tsutomu
Published: July 2006

The photolysis of androsterone oxime and 13α-androsterone oxime affords isomeric lactams with and without the original configuration of the C-13 substituent of the starting oxime, although there were poor yields and no products due to photo-Beckmann fission. The formation of an epimeric pair of lactams from an oxime is at variance with our previous results on the photolysis of 5α- and 5β-cholestan-6-one oximes, in which the stereochemical integrity of the terminus of the migrating carbon in the photo-Beckmann rearrangement was observed. The implication of the present results for the migration step of the photo-Beckmann rearrangement is discussed.
The Chlorination of Olefins with Antimony(V) Chloride
Authors: Uemura Sakae , Onoe Akira , Okano Masaya
Published: July 2006

Antimony(V) chloride was revealed to be a good reagent for the cis-chlorination of simple olefins in chlorinated hydrocarbon solvents, such as 1,2-dichloroethane, dichloromethane, chloroform, and carbon tetrachloride. The higher the reaction temperature or the solvent polarity was, the higher the selectivity for cis-chlorination became. From 1,3-butadiene, cis-1,4-dichloro-2-butene was formed together with the trans-1,4- and 1,2-dichloro isomers. In the cases of cyclopentene and norbornene, the trans-1,2-dichloride and other various dichlorides were obtained without any formation of the cis-1,2-isomer. Probable mechanisms for this chlorination are briefly discussed.
Rotational Isomerism in Methyl-d-amine
Authors: Tamagake Keietsu , Tsuboi Masamichi
Published: July 2006

Infrared absorption spectra of methyl-d-amine and methyl-d-amine-d2 have been observed in their gaseous states. For each of seven vibrations of the former and seven vibrations of the latter, two Q-branch peaks are observed assignable to trans and gauche forms of the molecule. In the microwave absorption spectrum of methyl-d-amine 60 lines assignable to the trans form (whose rotational constants are A=86085, B=20546, and C=20475 MHz) and 140 lines assignable to the gauche form (A=86512, B=21243, and C=19911 MHz) are found. Every trans line shows an inversion doubling which is considered to reach an observable amount only through a trans-gauche mixing of the vibration-rotation wavefunctions. This trans-gauche mixing should in turn depend upon the energy difference ΔETG between the ground vibration-rotation levels of the trans and gauche forms. On the basis of the observed amount of the inversion splitting, ΔETG has been determined to be 6.7±0.4 cm−1. The ΔETG value has then been refined by observing an accidental degeneracy of the trans and gauche energy levels, so that ΔETG=7.06±0.03 cm−1.
Hole-particle Formalism for the Electronic Spectra of Long Chain Polyenes
Authors: Basu Sadhan
Published: July 2006

From the hole-particle description of the many-Fermion system of long chain polyenes it has been shown that the convergence limit in the electronic spectra may be accounted for by the electron-hole pairing interaction.
Very-high-dose-rate Radiolysis of n-Butane in the Gas Phase. The Effect of the Addition of Electron Scavengers
Authors: Hatano Yoshihiko , Takao Satoshi , Namba Hideki , Ueno Takumi , Shida Shoji
Published: July 2006

The dose rate and its pulse-to-pulse reproducibility of very-high-intensity electron pulses have been measured. The effect of the addition of electron scavengers on the neutralization processes in the gas-phase radiolysis of n-butane has been examined by using this very high dose-rate electron pulse.
Flash-Spectroscopic Study of Phthalazine
Authors: Kanamaru Nobuaki , Nagakura Saburo , Kimura Katsumi
Published: July 2006

The phthalazine triplet and the hydrogen-abstracted radical were obtained in ethanol etc. at room temperature, suggesting that the T1 is of nπ* type, whereas only the T–T absorption spectrum was obtained in acidic ethanol as reported in EPA glass at 77 K.
A Solvent-Extraction Study of Zinc(II) Complexes with Several Divalent Anions of Carboxylic and Inorganic Acids
Authors: Moriya Hiromitsu , Sekine Tatsuya
Published: July 2006

Stability constants of zinc(II) mono- and biscomplexes with C2 to C6 dicarboxylic acids and with sulfate, thiosulfate and selenate ions determined at 25 °C by solvent extraction are described. The stability order of the dicarboxylate complexes decreases in an order of C2>C3>C4\simeqC5\simeqC6 whereas that of the inorganic acids are nearly similar.
The Migration of Electronic Excitation Energy in Copolymers of N-Vinylcarbazole with a Small Content of Styrene or Vinyl Acetate
Authors: Okamoto Kenichi , Yano Akikazu , Kusabayashi Shigekazu , Mikawa Hiroshi
Published: July 2006

The migration of electronic excitation energy in films of copolymers rich in N-vinylcarbazole has been studied by fluorescence quenching experiments using dimethyl terephthalate and perylene as guest molecules. The efficiency of the singlet exciton migration is almost the same for the copolymers and for poly-N-vinylcarbazole.
INDO Calculation of 13C Chemical Shifts by the Finite Perturbation Method
Authors: Fukui Hiroyuki
Published: July 2006

The approximate SCF-MO calculation of 13C nuclear magnetic shielding constants was performed using the finite perturbation method. The results indicated that the INDO finite perturbation method calculates 13C chemical shifts in poor agreement with experiment.
Reactions of Tris(acetylacetonato)manganese(III) and -cobalt(III) with 1,10-Phenanthroline and α-Methylstyrene
Authors: Kaeriyama Kyoji
Published: July 2006

Lower-valence-state compounds, bis(acetylacetonato)manganese(II) and bis(acetylacetonato)(1,10-phenanthroline)manganese(II), were prepared from tris(acetylacetonato)manganese(III). ESR spectra of manganese(II)compounds were shown. Bis(acetylacetonato)(1,10-phenan-throline)Co(II) was also prepared. The results were compared with activity for the initiation of radical polymerization.
The Synthesis of Crystalline Hydrated Double Carbonates of Rare Earth Elements and Sodium
Authors: Mochizuki Akihiko , Nagashima Kozo , Wakita Hisanobu
Published: July 2006

Crystalline hydrated double carbonates of rare-earth elements and sodium were obtained by adding sodium carbonate solutions to rare-earth chloride solutions. The formula of the precipitates was determined to be LnNa(CO3)2·6H2O (Ln=La, Ce, Nd, Sm, Gd, Dy, and Y). The products have similar X-ray powder diffraction patterns, which were indexed assuming a tetragonal symmetry. The cell parameters of the products were calculated, they decrease linearly with the decrease in the ionic radii of the rare-earth elements.
Role of Germanate Catalyst in the Transformation of Germanium Dioxide
Authors: Yonemura Michiko , Kotera Yoshihide
Published: July 2006

The role of alkali germanates as catalysts in the polymorphic transformation of germanium dioxide was investigated by high-temperature X-ray diffraction method. Lithium germanate and sodium germanate catalyze the transformation in a solid state, the activation energies being larger than 80 kcal/mol. Potassium germanate catalyst plays its role in a liquid state, the activation energy being smaller than that of other catalysts.
Effect of Surrounding Atmosphere in the Transformation of Germanium Dioxide
Authors: Yonemura Michiko , Kotera Yoshihide
Published: July 2006

The effect of surrounding atmosphere on the phase transformation of germanium dioxide with alkali germanate catalysts was investigated by high temperature X-ray diffraction method. The catalysts were Li2O·7GeO2, 3K2O·11GeO2, K2O·7GeO2 and 2Na2O·9GeO2. The ambient atmospheres were dry or wet nitrogen and oxygen. The effect of atmosphere was found to be not so large as that of the catalyst. Water vapor has prominent effects upon the transformation as in other solid state reactions.
Characteristic Studies on Dealumination of Faujasite-type Zeolite
Authors: Tsutsumi Kazuo , Kajiwara Hisao , Takahashi Hiroshi
Published: July 2006

Aluminium ion was extracted stoichiometrically from the framework of the faujasite-type zeolite by EDTA treatment. Dealuminated zeolites with various silica/alumina ratios (from 4.80 to 10.29) were obtained. A dealuminated zeolite does not necessarily show the molecular-sieve-type adsorption isotherm of nitrogen. The lattice constant of zeolite decreases with the silica/alumina ratio. The zeolite with an increased silica/alumina ratio has a higher catalytic activity for a cumene-cracking reaction than the parent H-Y4.80 zeolite. It is suggested, on the basis of infrared spectroscopic and calorimetric measurements, that the total number of acid sites decreases with dealumination, while the number of strong acid sites increases. These strong aicd sites seem to contribute to the catalytic activity of dealuminated zeolite.
The Crystal Structure of 2,4,6-Triphenylpyrylium-1,1,3,3-tetracyanopropenide, [(C23H17O)+·(C7HN4)−]
Authors: Tamamura Toshiaki , Yamane Takashi , Yasuoka Noritake , Kasai Nobutami
Published: July 2006

The crystal structure of an organic charge transfer salt 2,4,6-triphenylpyrylium-1,1,3,3-tetracyanopropenide has been determined by means of X-ray diffraction. The crystals are monoclinic in the space group P21/a. The unit cell dimensions are: a=13.024, b=21.357, c=8.324Å, β=94.56°. The cation and the anion are nearly planar and form an “ion-pair.” The crystal is built up from infinite columns stacked by these ion-pairs along the c axis. Between two adjacent anions in the neighboring columns, a weak hydrogen bond (C–H···N 3.265 (5), H···N 2.185(4) Å) is present. The charge transfer interaction between the anion and the cation seems to have less influence on the crystal structure than the electrostatic force or the hydrogen bonding.
The Synthesis and Spectroscopic Study of Some Bis(tertiaryphosphine)bis(N,N-dialkylselenocarbamate) Complexes of Palladium(II) and Platinum(II)
Authors: Tanaka Koji , Tanaka Toshio
Published: July 2006

Ten N,N-dialkylselenocarbamate complexes of palladium(II) and platinum(II), [(C6H5)3P]2Pd[SeC(O)NR2]2(1), [(C6H5)3P]2Pt[SeC(O)NR2]2 (2) (R=CH3, C2H5, n-C3H7, and n-C4H9), [CH3(C6H5)2P]2Pd[SeC(O)N-(CH3)2]2 (3), and [CH3(C6H5)2P]2Pt[SeC(O)N(CH3)2]2 (4), have been prepared. The infrared spectra and molecular-weight determinations indicate that the selenocarbamate ligand is bonded to the palladium(II) or platinum(II) through the selenium atom, with a free carbonyl group in the solid state, while in 1 and 2 two and one triphenylphosphine dissociate in a dilute solution to exist as compounds with bidentate selenocarbamate, Pd[SeC(O)NR2]2 and [(C6H5)3P]Pt[SeC(O)NR2]2, respectively. The 1H- and 31P-NMR spectra of 3 and 4 reveal that they have a trans-configuration. The same configuration is suggested for the N,N-dibutyl derivative of 2 on the basis of the spin-spin coupling constant between the 31P and 195Pt nuclei.
Bromine Addition Reaction to Olefins with Magnesium Bromide and Aroyl Peroxides
Authors: Okubo Masao , Kusakabe Hisahiro , Hiwatashi Tsunenori , Kishida Kazuo
Published: July 2006

When MgBr2 prepared in anhydrous tetrahydrofuran was added to a mixture of olefin and benzoyl peroxide, the peroxide decomposed at a moderate rate at room temperature. Olefin dibromide and magnesium benzoate were obtained in nearly quantitative yields. The effects of p- and m-substituents of peroxide and of the structure of olefin were studied. A complex consisting of MgBr2 and peroxide was formed. Abstraction of brominium cation from the complex by the olefinic double bond was proposed.
Products Obtained by the Reaction of Trichlorotrimethylbenzenes with Fuming Nitric Acid. Side-chain Nitrooxylation versus Oxidation to Unsaturated Cyclic Ketones
Authors: Suzuki Hitomi , Maruyama Shigeru , Hanafusa Terukiyo
Published: July 2006

The reaction of trichlorotrimethylbenzenes with fuming nitric acid has been investigated. Trichloropseudocumene underwent both side-chain nitrooxylation and nuclear oxidation to give 2,5,6-trichloro-3,4-dimethylbenzyl nitrate, 3,5,6-trichloro-2,4-dimethylbenzyl nitrate, and 3,6-dichloro-4-nitro-2,4,5-trimethylcyclohexa-2,5-dienone. Trichloromesitylene yielded a mixture of several carbonyl compounds, from which 3,5-dichloro-4-hydroxy-2,4,6-trimethylcyclohexa-2,5-dienone and two nitro-ketones, tentatively formulated as 2,4,6-trichloro-5-hydroxy-6-nitro-2,3,5-trimethylcyclohex-3-enone and 3,5-dichloro-2-hydroxy-6,6-dinitro-2,4,5-trimethylcyclohex-3-enone, were obtained as crystalline products by chromatography and fractional extraction. Trichlorohemimellitene behaved similarly towards the nitrating agent to give 2,6-dichloro-4-hydroxy-3,4,5-trimethylcyclohexa-2,5-dienone as the major product. The competitive modes of side-chain nitrooxylation and formation of cyclic ketones have been described.
Theoretical Considerations of Lower Excited States of trans-Polyene Carbaldehydes. I. Electronic Structure and Oscillator Strength of π–π* Transition
Authors: Inuzuka Kozo , Becker Ralph S
Published: July 2006

The lower n,π* and π,π* excited state energies of four tomj-polyenecarbaldehydes, acrolein, 2,4-pentadienal, 2,4,6-heptatrienal, and 2,4,6,8-nonatetraenal, were calculated within the framework of the conventional P-P-P SGF-MO-CI method and then discussed. Also, the oscillator strength for the π,π* transition was obtained in terms of the dipole length and the dipole velocity.
The Phenanthrene/Anthracene–Picric Acid System
Authors: Koizumi Shigeo , Matsunaga Yoshio
Published: July 2006

The phase relations in the phenanthrene/anthracene–picric acid system have been determined by calorimetry and X-ray diffraction. Four series of solid solutions occur in this system: the terminal solid solutions P and A, which are based on the parent picrate lattices, and the I and II solutions, which are based on the incongruentlymelting ternary compounds. A eutectic is observed at about 47 mol% anthracene and at 124 °C. Enantiotropic transitions appear at about 76, 103, and 120 °C in the I solid solution and at about 80, 103, and 120 °C in the II solid solution. The Gibbs energy of formation from the solid component compounds has been estimated as −2.04, −1.67, −1.21, and −0.68 kcal/mol for the stable forms at the room temperature of the phenanthrene picrate, the I solid solution (at 34.58 mol% anthracene), the II solid solution (at 58.96 mol%), and the anthracene picrate respectively. The two transitions in the phenanthrene picrate have been shown to be easily detectable by recording the electrical resistivity as a function of the temperature.
Synthesis and Reactions of 4-Dimethylsulfuranylidene-2,3-dioxotetrahydrofuran Derivatives
Authors: Hagio Katsuaki , Yoneda Naoto , Takei Hisashi
Published: July 2006

The cyclic sulfonium ylides, 4-dimethylsulfuranylidene-2,3-dioxotetrahydrofuran derivatives (8), were synthesized in good yields by reactions of methyl and ethyl dimethylsulfuranylidenepyruvates (3 and 4) with carbonyl compounds. The reactions of 8 with p-toluenesulfonyl chloride and benzoyl chloride gave 4-methylthio-3-(p-toluenesulfonyloxy)- and 4-methylthio-3-benzoyloxy-2-oxo-2,5-dihydrofuran derivatives respectively in high yields. The ylides (8) reacted with mercaptans to afford 4-substituted products (14–16), whereas, on the reactions with thiourea, the demethylation of the dimethylsulfonium group proceeded exclusively.
Synthesis of 6-(2-Amino-2-deoxy-β-d-glucopyranosylamino)- and 6-(β-d-Glucopyranosylamino)purine
Authors: Fukatsu Shunzo , Sawa Aiko , Umezawa Sumio
Published: July 2006

6-(β-Glycosylamino)purines have been synthesized in good yields by condensation of 4-amino-5-nitro-6-chloropyrimidine with masked glycosylamines followed by hydrogenation of nitro group, cyclization with triethyl orthoformate and removal of protecting groups.
Interaction between Carbon Dioxide and the Zinc Oxide Surface
Authors: Morimoto Tetsuo , Morishige Kunimitsu
Published: July 2006

The adsorption of carbon dioxide has been measured at 25°C on zinc oxide surfaces with different amounts of preadsorbed carbon dioxide. As a result, it has been found that carbon dioxide molecules are chemisorbed more weakly to zinc oxide surfaces than water; the desorbability of carbon dioxide is almost complete upon evacuation at temperatures higher than 300 °C, whereas upon evacuation at 25°C 80% of the carbon dioxide remains on the surface. Also, the adsorption isotherms of carbon dioxide have been obtained at 25°C on differentlyhydroxylated surfaces of zinc oxide. On such surfaces, the adsorption amount of carbon dioxide decreases linearly with an increase in the amount of surface hydroxyl groups. This suggests that most of the carbon dioxide is adsorbed strongly on the vacant sites formed by dehydroxylation, and not on the surface hydroxyl groups.