Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 53 , Issue 12
Showing 1-50 articles out of 71 articles from the selected issue
  • Mamoru Ai
    1980 Volume 53 Issue 12 Pages 3391-3394
    Published: 1980
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    The numbers of both acidic and basic sites in a series of Bi2O3-XnOm binary oxides, with different kinds and amounts of the second component, XnOm, were systematically determined by means of the adsorption of NH3 and CO2 from the gas phase, using the static method. Pure Bi2O3 has both acidic and basic sites, much like TiO2, SnO2, and Fe2O3, and it is more basic than these oxides. The generation of an unexpectedly high acidity or basicity was not observed in the combination of Bi2O3 with 11 kinds of oxides, and the acid-base properties of the binary oxides can be understood in terms of the nature of the second component. The order of ability for the promotion of the acidity and the diminution of the basicity is: MoO3, SO3, WO3>V2O5, P2O5>Sb2O4>TiO2, SnO2, Fe2O3. The addition of K2O decreases the acidity and increases the basicity. The relationship between the acid-base properties and the catalytic activities for the isomerization of 1-butene, the dehydration and dehydrogenation of 2-propanol, and the oxidative decomposition of formic acid was investigated. It was proposed that the basic sites of the Bi2O3based mixed oxides originate from Bi2O3 and that the nature remains approximately the same, regardless of any change in the kind and amount of the second component. However, the acidic sites are generated by the combination with second component; therefore, the nature varies widely depending on the nature of the second component.
  • Masaru Nakahara, Yasuhiro Uosaki, Muneo Sasaki, Jiro Osugi
    1980 Volume 53 Issue 12 Pages 3395-3399
    Published: 1980
    Released: April 19, 2006
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    The electronic, 13C NMR, 1H NMR, and IR spectra of the 1,4-cycloadducts of TCNE with styrene, styrene-α-d1, p-chlorostyrene, p-methylstyrene, α-methylstyrene, and 1,1-diphenylethylene were taken at low temperatures at 1 bar after the high-pressure reaction; the 13C NMR spectra were of decisive importance in determining the structure; the other kinds of spectra were consistent with the established structure. They have an electronic absorption band around 320 nm, which is assigned to the π-π* transition of the triene system in the adducts. Neither cis- nor trans-stilbene, which have a lower ionization potential, provides the 1,4-cycloadduct even at high pressure.
  • Tatsuo Takahashi, Takefumi Koiso
    1980 Volume 53 Issue 12 Pages 3400-3403
    Published: 1980
    Released: April 19, 2006
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    The kinetics of the complex-formation reactions of Ni(II) with 4-phenylpyridine, isoquinoline, 2,2′-bipyridine, 1,10-phenanthroline, and 2,2′: 6′,2″-terpyridine in water-t-butyl alcohol mixtures were investigated by means of stopped-flow measurement. With an increase in the t-butyl alcohol content of mixtures for all ligands, the rate constants for the reactions decrease monotonically, while the activation parameters, ΔHf\ eweq and ΔSf\ eweq, pass through distinct minimum values, and the minima occur at the same concentration of t-butyl alcohol. The results are briefly discussed in terms of the stability of the outer-sphere complex of Ni(II) with the ligands, and the structural properties of the solvents.
  • Jun-ichi Aihara
    1980 Volume 53 Issue 12 Pages 3404-3407
    Published: 1980
    Released: April 19, 2006
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    For analogous normal vibrations in conjugated systems of a similar type a linear relationship often exists between vibrational frequencies and bond orders. We find that this linearity can, in principle, be extended to include conjugated systems in both excited electronic states and ionic states. This indicates that the linearity covers a full range of bond order conceivable for conjugated systems. Such an aspect of molecular vibrations gives a concise and sometimes decisive clue not only to vibrational assignments but also to structural analyses of conjugated systems in various electronic states. Symmetric C=C stretching vibrations of ethylene and tetracyanoethylene nicely illustrate this situation.
  • Yasumasa J. I’Haya, Yasunobu Oikawa, Tomoyasu Nakamura
    1980 Volume 53 Issue 12 Pages 3408-3413
    Published: 1980
    Released: April 19, 2006
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    Two types of circular dichroism (CD) spectra are found to be induced in the solution systems of α-chymotrypsin (αCT) and dyes. One is a single positive CD band which is due to a 1 : 1 αCT–dye complex (Type I; proflavine, Acridine Yellow G, acriflavine), and the other consists of one positive and one negative CD bands which are mainly due to a complex of the composition, one αCT to two dye molecules (Type II; Pyronin B, Rhodamine 6G). Mechanisms of CD induction tentatively proposed are that in Type I complexes a single dye molecule is bound to an asymmetric environment of the active site of αCT while in Type II complexes two dye molecules are bound at a specific site exerting a dipole-dipole interaction with one another.
  • Yoshiteru Hayami, Takeshi Yano, Kinsi Motomura, Ryohei Matuura
    1980 Volume 53 Issue 12 Pages 3414-3417
    Published: 1980
    Released: April 19, 2006
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    In order to clarify the behavior of mixed monolayers of butyl eicosanedioate and tetradecanoic acid, the surface pressure was measured as a function of mean area at various compositions and temperatures. Four types of phase transition were observed. By use of the thermodynamic treatment previously developed, the apparent molar entropy and energy changes associated with the phase transition were evaluated. It was concluded on thermodynamic considerations that the butyl eicosanedioate and tetradecanoic acid monolayers are immiscible in condensed states and their phase diagram has a two-dimensional eutectic point.
  • Shigeyuki Aono, Kiyoshi Nishikawa
    1980 Volume 53 Issue 12 Pages 3418-3423
    Published: 1980
    Released: April 19, 2006
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    The electronic structures of molecules composed of identical atoms are investigated in terms of propagators under the Hückel approximation. General rules to get propagators for systems under considerations are presented. Then some physical quantities (the charge densities, the bond orders and the total energies) are obtained by making the analysis of the propagators. Expressions for the mutual polarizabilities are also exactly derived. Some discussions about the approximate natures of current results are made.
  • Kazuo Sasaki, Akira Kitani, Atsutaka Kunai, Hitoshi Miyake
    1980 Volume 53 Issue 12 Pages 3424-3429
    Published: 1980
    Released: April 19, 2006
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    A model system of the NADH/FAD redox couple has been studied by the use of electrochemical techniques. The system studied was composed of 1-benzyl-1,4-dihydronicotinamide (BNAH) and riboflavin (RF), which were used in place of NADH and FAD respectively, dissolved in a DMSO solution. The results obtained were as follows. RF is reduced either by BNAH or sodium borohydride, obeying a second-order rate law, presumably by the mechanism of hydride-ion transfer. The resultant product is inactive to the electrochemical reduction at a mercury-pool electrode. Entirely different products were produced when RF was reduced electrochemically. RF was reduced at a rate of 1 F/mol at the initial stage of controlled potential electrolysis to form, probably, a dimeric compound, but the latter product underwent further reduction and the total quantity of electricity necessary for the complete reduction exceeded 10 F/mol. Interestingly, the electrolytic reduction gives the same product as that obtained by BNAH when electrolysis is performed in the presence of a sufficient amount of BNAH, indicating that the initial product of electrochemical reduction receives the hydride ion rather than further electrons.
    2RF+2e\ ightleftarrows(RF)_2^2-\overset+H^-,+H^+→2RFH^-
    The Zn2+ added to the BNAH/RF system was found to act as the oxidizing agent of RFH and regenerated the neutral RF. This is markedly different from the case of BNAH/organic carbonyl compounds, where the metal ions behave as catalysts to promote the reaction.
  • Masashi Tanaka, Atsushi Watanabe, Jiro Tanaka
    1980 Volume 53 Issue 12 Pages 3430-3435
    Published: 1980
    Released: April 19, 2006
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    Optical absorption and reflection measurements are carried out on pure and ClSO3H doped polyacetylene films over a wide wavelength region (350–35000 cm−1). In the doped polymer, the transition from the valence band to the impurity level is observed at 870 cm−1 and the free carrier absorption band appears over the wide region of 350 to 20000 cm−1, while the interband transition located in the region of 15000 cm−1 disappears. This means that doping removes the bond alternation leading to a uniform bond length and all π-electrons contribute to the transport. For the heavily doped films, the d.c. conductivity of polyacetylene films is obtained by the optimum fit of the theoretical curve to the observed absorption and reflection spectra. The obtained values are comparable with the d. c. conductivity (σ\simeq280–250 Ω−1 cm−1) obtained by the four probe method.
  • Yoshihisa Yamamoto, Zenjiro Kanda
    1980 Volume 53 Issue 12 Pages 3436-3438
    Published: 1980
    Released: April 19, 2006
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    Alkoxymethyltriphenylphosphonium salts, [(C6H5)3PCH2OR]X, X: Cl, Br, and I, R: CH3, C2H5, and i-C3H7, have been obtained from the reaction of the triphenylphosphine and the corresponding alkyl halomethyl ether. In the 13C-NMR spectra of these salts, the coupling constant (JCP) is 68–71 Hz, which is larger than that (JCP: 48–56 Hz) of [(C6H5)3PCH2R]Br, R: H, CH3, and i-C3H7, Me3P=S and Me3P=Se, while it is close to that(66–69 Hz) of Me3P=O and Et3P=O. The coupling constant (JCP) of these salts can be caused by the oxygen atom in the salts.
  • Hiroaki Matsuda
    1980 Volume 53 Issue 12 Pages 3439-3446
    Published: 1980
    Released: April 19, 2006
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    A general theory of pulse polarographic current-potential curves is developed for a simple electrode reaction proceeding at the expanding plane electrode. It is shown that when the ratio of the sampling time to the pre-electrolysis time is smaller than 1/30, this condition being satisfied in usual pulse polarographic practice, the equation of current-potential curves can be greatly simplified. The theory developed is applied to the three modes of pulse polarography nowadays practically employed, i.e., normal pulse, scan-reversal pulse and differential pulse polarography. For each mode, the dependence of current-potential curves on the kinetic parameters of electrode reaction as well as on the experimental variables is discussed.
  • Seiichiro Koda, Yasushi Ohnuma, Tadashi Ohkawa, Soji Tsuchiya
    1980 Volume 53 Issue 12 Pages 3447-3456
    Published: 1980
    Released: April 19, 2006
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    The multiple photon dissociation of cyclobutanone was discussed on the basis of the observed relative significance of two reaction channels. Cyclobutanone was irradiated by a TEA CO2 laser beam of 9.6 μm R(14) line in a parallel and a focussed geometry. The detected products were ethylene, ketene, and cyclopropane under parallel geometry irradiation. Propylene and acetylene were also produced in focussed geometry irradiation. The kind of the products as well as the effects of reaction conditions on their yields led to the conclusion that the dissociation proceeds along two channels, in one of which ethylene and ketene are produced and in the other cyclopropane and CO. The experimental results agreed almost with the result simulated by a statistical model calculation based on the hypothesis that the energy absorbed in cyclobutanone molecules is statistically distributed among all vibrational degrees-of-freedom.
  • Harutoshi Sakai, Toshihiko Fujimori, Yoshio Imamura
    1980 Volume 53 Issue 12 Pages 3457-3461
    Published: 1980
    Released: April 19, 2006
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    The configuration of poly(methyl methacrylate) adsorbed on silica from dilute solution (CCl4, benzene, and CHCl3) was studied from the point of view of the chain motion by a spin-labeling technique. The ESR spectrum of the adsorbed polymer was found to be composed of three portions, which had considerably different degrees of the motional freedom of the local chain segments. The rotational correlation times corresponding to the three portions were estimated by the line shape analysis and the rapid passage technique. These times were 1×10−9, 5×10−9, and longer than 10−6 s, and were attributed to the motions in the long loop, short loop, and train, respectively. The large fractions of the bound segments, obtained in all the cases of low surface coverage, showed highly flattened structures of the adsorbed chain molecules. In the adsorption from a poor solvent (CCl4), a strongly compressed structure with a large number of the short loops was found. The adsorbed layer thickness, indicated by the fraction of the segments in the three states, became much smaller with an increase in the solvent power and a decrease in the surface coverage.
  • Noboru Imai, Yoji Arata, Shizuo Fujiwara
    1980 Volume 53 Issue 12 Pages 3462-3467
    Published: 1980
    Released: April 19, 2006
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    The surface of the iron core of ferritin was investigated by 1H NMR using small probe molecules which have different sizes and charges. It was shown that the parameter k, which is the linewidth for each NMR probe normalized by the total concentration of iron in ferritin, is dependent on the content of phosphorus in ferritin. At pH 7.4, the k values are 1–10 for positively charged probes, 2×10−2–8×10−2 for negatively charged probes and 0.1–0.2 for neutral probes. Above pH 7, the k values for positively charged probes increase with an increase in pH, whereas those for negatively charged probes decrease. By contrast, the k values for neutral probes remain constant over the entire pH range. It was concluded that the k values reflect the mode of interactions of small molecules with the phosphate which exists on the surface on the iron core of ferritin, and that these interactions are determined primarily by the electrostatic force between the small molecules and the negative charge of the phosphate of ferritin. Furthermore, it was shown by using t-butylamine as a probe that K+ ion binds strongly to ferritin and that chelating agents interact with ferritin in a wide concentration range.
  • Yukio Kubota, Yuko Motoda
    1980 Volume 53 Issue 12 Pages 3468-3473
    Published: 1980
    Released: April 19, 2006
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    The interaction of the mutagenic dye 9-aminoacridine (9AA) with polyriboadenylic acid (poly rA) was studied by both steady-state and transient fluorescence measurements. It was found that the fluorescence decay of 9AA bound to poly d(A-T) follows a single-exponential decay law but that the decay data of 9AA bound to poly rA can be well described as a sum of two-exponential functions. The fact that nanosecond time-resolved fluorescence spectra are independent of time suggests that the double-exponential decay may be attributed to different microenvironments at the binding sites. The decay parameters, fluorescence emission maxima, and fluorescence quantum yields obtained at acid pH differ from those obtained at neutral pH. The fluorescence behavior of 9AA is discussed in connection with the conformational change of poly rA.
  • Kenji Yokoyama, Junko Nakamura, Takayoshi Kobayashi, Saburo Nagakura
    1980 Volume 53 Issue 12 Pages 3474-3477
    Published: 1980
    Released: April 19, 2006
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    By irradiation with a focused laser beam, p-nitroanisole and N-[2-(p-nitrophenoxy)ethyl] aniline (2) in acetonitrile were found to show new reactions yielding nitroso compounds different from the case of the defocused laser beam irradiation. The laser intensity dependence of the product yield shows that the new reaction of 2 proceeds via a biphotonic process. The quenching effects of oxygen and cis-1,3-pentadiene upon the reaction rate indicate that the intermediate state is an excited singlet state.
  • Fumiyuki Mitsumori, Yoji Arata, Shizuo Fujiwara
    1980 Volume 53 Issue 12 Pages 3478-3482
    Published: 1980
    Released: April 19, 2006
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    Interaction between penicillin G and hen egg white lysozyme has been studied using NMR and gel chromatography. It has been demonstrated that the stoichiometry of the interaction is one to one with an association constant of approximately 1.9×102 M−1 (1M=lmol dm−3). It has also been shown that the phenacyl side chain of penicillin G is interacting with the tryptophan-123 residue of the lysozyme molecule.
  • Tetsuo Uechi, Hiroko Yamaguchi, Ikuhiko Ueda, Kazuo Yasukouchi
    1980 Volume 53 Issue 12 Pages 3483-3487
    Published: 1980
    Released: April 19, 2006
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    The crystal and molecular structure of the red compound, [(NH4)Cu3Cl4(C6H4O2)1.5·H2O], has been determined from 2115 X-ray diffraction data collected on an automated four-circle diffractometer. The crystals are monoclinic, with space group P21/c, and with four formula units in a unit cell of dimensions; a=7.308(5), b=11.593(7), c=18.359(9) Å, and β=90.16(3)°. The structure was solved by direct methods, and block-diagonal leastsquares refinements led to a final discrepancy index, R, of 0.035. The crystal structure is characterized by polymeric, beehive-like layers composed of Cu3Cl4 anions, and centro- and pseudocentrosymmetric p-benzoquinone molecules. Each of the p-benzoquinone molecules acts as a bridging ligand to the two trans Cu3Cl4 anions, with the Cu–C closest distances falling in the range from 2.047(5) to 2.086(5) Å. The NH4+ cations and the water molecules are accommodated by a roughly coplanar arrangement within the tunnel-like holes of the beehives, and the NH4+ cations are joined to the layers by intra- and interlayer hydrogen bonds of the N–H···O type. The Cu3Cl4 has a distorted cubane-type structure with one corner missing, and each Cu atom has a distorted tetrahedral coordination.
  • Kanichi Shimada, Toshikazu Tarutani
    1980 Volume 53 Issue 12 Pages 3488-3491
    Published: 1980
    Released: April 19, 2006
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    The process of the polymerization of silicic acid can be divided into three steps: (1) a reaction between monosilicic acids, (2) a reaction between monosilicic and polysilicic acids, and (3) a reaction between polysilicic acids. The rates of the reactions between monomer-monomer, monomer-polymer and polymer-polymer are most rapid at pH values around 9.3, 8.5, and 6.8 respectively. It is concluded that, above about pH 4, the polymerization due to Reactions 1, 2, and 3 proceeds mainly by a reaction between ionized and un-ionized silanol groups.
  • Yoshihiro Mori, Taiji Kitagawa, Tomoki Yamamoto, Kazuo Yanada, Shigeru ...
    1980 Volume 53 Issue 12 Pages 3492-3495
    Published: 1980
    Released: April 19, 2006
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    Characteristic ions (M+1)+ and (M+45)+, assigned to be the protonated monomer ion MH+ and (M·CO2H)+ respectively, have been detected in the mass spectrometric measurements of the dimer molecules M2 and the higher clusters Mn of some carboxylic acids produced in their nozzle beams. It has been shown from the dependences of their relative intensities on the stagnation conditions that these ions are mainly formed through the fragmentation of the dimer ions. The MH+ ion plays the most important role in these fragmentation processes of the dimers, while no dimer ion M2+ was observed. These results are discussed in terms of the enthalpy changes for the unimolecular decomposition reactions of M2+.
  • Nobuaki Washida, Hajime Akimoto, Michio Okuda
    1980 Volume 53 Issue 12 Pages 3496-3503
    Published: 1980
    Released: April 19, 2006
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    An attempt was made to detect O2*(a1Δg) in the reactions of O+O3, H+O3, and NO+O3 using a photoionization mass spectrometer. No significant signals for O2*(a1Δg) were observed in these reactions. From the results, it is concluded that less than 0.06, 0.001, and 0.002 of the reactive collisions result in the production of O2*(a1Δg) in the reactions of O+O3, H+O3, and NO+O3 respectively, all at 298 K. The failure to observed O2*(a1Δg) in these reactions was discussed by means of correlation diagrams and GVB model representations.
  • Mutsuaki Murakami, Susumu Yoshimura
    1980 Volume 53 Issue 12 Pages 3504-3509
    Published: 1980
    Released: April 19, 2006
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    N-Propylpyridinium (TCNQ)x crystallized in two complex salts (x=2, 2.5), both of which displayed initial irreversible and subsequent reversible first-order phase transitions with a sharp discontinuity in the electrical conductivity. The reversible transitions of both salts are essentially the same in spite of their differences in stoichiometry. The transitions were accompanied by crystal structure changes; the changes in the physical properties were ascribed to the crystalline distortion in both the one-dimensional TCNQ chain and the motion of the cation molecules. The high-temperature phase was metallic, with a zero activation energy for conduction; the source of the metallic behavior was also discussed. The electronic and infrared absorption spectra suggest that the high-temperature modification has a less distorted stacking of TCNQ molecules in the column.
  • Masayuki Matsumoto, Kazuo Amaya
    1980 Volume 53 Issue 12 Pages 3510-3512
    Published: 1980
    Released: April 19, 2006
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    The heats of solution of crystalline amino acids and hydroxy acid in water at 298.15 K were measured with a twin isoperibol calorimeter. It was found, as was expected from the theory, that the difference in the heat of solution between optically active compounds and their corresponding racemic compounds was appreciably large compared with the heat of mixing of concentrated aqueous solutions of d- and l-optical isomers.
  • Kazuhiko Ishizu, Tokuhiro Haruta, Yuji Kohno, Kazuo Mukai, Kiyonori Mi ...
    1980 Volume 53 Issue 12 Pages 3513-3516
    Published: 1980
    Released: April 19, 2006
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    Copper(II) chloride and crown ethers (12-crown-4, 15-crown-5 and 18-crown-6) formed orange or orangeyellow complexes in dry chloroform. We found that the ESR g-anisotropy of the complexes was greatly dependent on the numbers of donor oxygens and the ring-numbers. The complexes obtained from 12-crown-4 and 18-crown-6 showed g-anisotropy (g⁄⁄>g); these are well characterized by the 3dx2−y2, or 3dxy ground state. On the other hand, the complexes of 15-crown-5 and its benzo derivatives exhibited the reverse g-anisotropy (g⁄⁄<g); these are characterized by the 3dz2 ground state with S=1/2. The electron nuclear dipolar term and the Fermi’s isotropic term were estimated from the ESR parameters based on Bleaney’s calculation. The chlorine superhyperfine splittings were observed in the g⁄⁄- component. The MO bonding parameters were estimated by assuming the compressed octahedral, the trigonal bipyramidal, and pentagonal bipyramidal geometry at the paramagnetic site. The bonding nature was studied on the basis of the observed ligand spin densities.
  • Yoshihisa Yamamoto, Eiko Toyota, Naoto Mitsudera
    1980 Volume 53 Issue 12 Pages 3517-3521
    Published: 1980
    Released: April 19, 2006
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    The picrate of the paramagnetic, [Co(5-NO2sal)(bpy)2]2+, has been isolated from a reaction mixture of picric acid, 60% nitric acid, and bis(2,2′-bipyridine)(salicylato)cobalt(III) chloride trihydrate, [Co(sal)(bpy)2]Cl·3H2O, which had been prepared from salicylic acid and cis-bis(2,2′-bipyridine)dichlorocobalt(III) chloride dihydrate. The absorption spectrum and the stability of an aqueous solution of the picrate of the paramagnetic, [Co(5-NO2sal)(bpy)2]2+, were somewhat different from those of complexes of the paramagnetic, [Co(5-NO2sal-R)(NH3)4]2+ (R: H, CH3). Several complexes of the paramagnetic, β1-5-nitrosalicylato-, β2-5-nitrosalicylato-, and β2-3-methyl (and 4-methyl)-5-nitrosalicylato(triethylenetetramine)cobalt(III) have, analogously, been isolated from reaction mixtures of 60% nitric acid and β1-salicylato-, β2-salicylato, or β2-methylsalicylato(triethylenetetramine)cobalt(III) chloride hydrate respectively. Their β1 and β2-isomeric forms were proved by a study of their IR and 1H-NMR spectra. From the IR, NMR, and the magnetic susceptibility measurement results, these compounds are considered to have the paramagnetic complex, [Co(5-NO2sal)L]2+(L: (NH3)4, (en)2, (bpy)2, and trien), and the electron hole is considered to delocalize over the chelate ring containing the cobalt atom and the 5-nitrosalicylato ligand.
  • Kengo Uchida, Yoshinobu Takinami
    1980 Volume 53 Issue 12 Pages 3522-3525
    Published: 1980
    Released: April 19, 2006
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    The kinetics of the trans-cis isomerization of [Cr(mal)2(H2O)2] have been investigated in binary mixed solvents, including methanol-, ethanol-, dioxane-, and acetone-water mixtures. The first-order rate constant increases with a decrease in the volume percentage of the water, but is independent of the kind of organic solvent. The rate is not affected by the addition of any cation to an aqueous solution. These results are in contrast to those for the analogous oxalato complex, and are interpreted in terms of a dissociation mechanism in which the rate-determining step is the dissociation of the coordinating water molecule.
  • Noboru Yoshida, Masatoshi Fujimoto
    1980 Volume 53 Issue 12 Pages 3526-3530
    Published: 1980
    Released: April 19, 2006
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    The proton-transfer reactions of bis(dimethylglyoximato)cobalt(III) complex ions, [CoIII(dmgH)2X2]n, with hydroxide ion, OH, were studied in dioxane–water media by means of a temperature-jump method. The rate constant, kf, for the direct proton-transfer from [CoIII(dmgH)2X2]n to OH was found to be 1.6×105–2.9×106 mol−1 dm3 s−1 in aqueous solution. The value of kf for [CoIII(dmgH)2(CN)2] anion decreased gradually from 1.6×105 to 4.0×104 mol−1 dm3 s−1 for the change in the mole fraction of dioxane, xdiox, from 0 to 0.174. On the other hand, with increase in xdiox, the value of kf for [CoIII(dmgH)2(NH3)2]+ cation gradually decreased from 2.9×106 to 1.1×107 mol−1 dm3 s−1 in a region of lower xdiox, and then increased from 1.1×106 to 1.6×106 mol−1 dm3 s−1 in a region of higher xdiox. The dependence of kf on xdiox is interpreted in connection with reaction mechanism.
  • Masami Saito, Takashi Uehiro, Yukichi Yoshino
    1980 Volume 53 Issue 12 Pages 3531-3536
    Published: 1980
    Released: April 19, 2006
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    A new method for hydrothermal syntheses of osmium(III), ruthenium(III), iridium(III), and rhodium(III) complexes with ethylenediaminetetraacetic acid (EDTA) and propylenediaminetetraacetic acid (PDTA) has been developed. More than ten new complexes have been obtained in good yields and characterized by measuring their magnetic susceptibilities, infrared and electronic spectra, and acid-base properties. The stereochemical behavior of the iridium(III) and rhodium(III) complexes has also been described.
  • Yuki Fujii, Katsuji Shiono, Kuniko Ezuka, Takashi Isago
    1980 Volume 53 Issue 12 Pages 3537-3546
    Published: 1980
    Released: April 19, 2006
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    Under air-oxidation conditions, the reaction of [Co(α-Me-sal2en)] with L-aaH, where α-Me-sal2en represents the dianion of N,N′-ethylenebis(α-niethylsalicylideneaniine) and where L-aaH denotes L-proline, hydroxy-L-proline, or allo-hydroxy-L-proline, proceeded rapidly to yield Λ-cis2–[Co(α-Me-sal2en)(L-aa)] stereoselectively, followed by the slow isomerization of the Λ-cis2-isomer thus formed to give the corresponding Δ-cis2-isomer in a yield of almost 100% under equilibrium conditions. The complexes thus formed were isolated and characterized by the use of their absorption, circular dichroism, and 1H-NMR spectra. The preferential formation of the Λ-cis2-isomer in the initial reaction was found to be kinetic in origin. The kinetic stereoselectivity was determined to be 87% for L-proline, 56% for hydroxy-L-proline, and 23% for allo-hydroxy-L-proline by the measurement of the rotation at 435 nm of the reaction solutions. On the other hand, no kinetic differentiation was observed for the formation of the similar cis2-complexes with L-alanine, L-valine, L-methionine, L-phenylalanine, L-tryptophan, N-benzyl-L-alanine, and N-methyl-L-alanine. On the basis of these data, the mechanism of the initial complexation was discussed. The high thermodynamic stereoselectivity for Δ-cis2-isomer was explained in terms of the intramolecular steric interaction between the pyrrolidine ring of the coordinated L-aa and the distorted α-Me-sal2en ligand in the complex.
  • Yuriko Abe, Goro Wada
    1980 Volume 53 Issue 12 Pages 3547-3551
    Published: 1980
    Released: April 19, 2006
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    The absorption spectra and Stokes radii of solvated complex ions of first transition metals (Mn(II), Fe(II), Co(II), Ni(II), Cu(II), and Zn(II)) were observed in hexamethylphosphoric triamide (HMPA) in order to determine their configurations. It seems that the Stokes radii of complex ions are sensitive to the configurational change, since the diameter of an HMPA molecule is very large as compared with the crystallographic diameters of central metal ions. As to the result, metal ions are tetrahedrally solvated in the cases of Mn(II), Fe(II), Co(II), and Cu(II), while in the case of Ni(II), equilibria are established among octahedral, square planar and tetrahedral solvated species. Zn(II) forms probably a complex ion solvated octahedrally by HMPA.
  • Etsuro Kobayashi, Tadao Kanayama
    1980 Volume 53 Issue 12 Pages 3552-3559
    Published: 1980
    Released: April 19, 2006
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    In order to develop an inorganic ion exchanger for industrial use, a mixture of titanium(IV) bis (hydrogenphosphate), a carbonaceous material (sugar, flour, or sodium ligninsulfonate), and an additive (H2SO4 or H3PO4) was sintered, and the resultant sintered product was crushed to obtain a granulated product, the ion-exchange property of which was then investigated. The mixing ratio of the titanium phosphate to the carbonaceous material has an influence on the ion-exchange capacity and the durability of the granulated product. In consideration of this influence, the weight ratio of the titanium phosphate to carbon included in the carbonaceous material was expediently chosen as 1 : 0.5. The acid additives promoted the carbonization of the carbonaceous material, whereby the sintered product of porosity was obtained. The weight ratio of the carbonaceous part to the titanium phosphate in the product decreased with an increase in the temperature within the range from 185 to 350 °C. In a batch method, a granulated product including Ti(HPO4)2·H2O adsorbed Na+, but not K+. A granulated product including Ti(HPO4)2·1/2H2O, however, adsorbed these ions, the equilibrium ion-exchange capacities toward Na+ and K+ being 1.28–1.78 and 1.56–2.34 meq/g respectively, and the selectivity quotient and the distribution coefficient toward K+ showed larger values than those toward Na+. In a column method, when a NaCl (26.66 g/l)KCl (0.67 g/l) aqueous solution flowed into a column which had been packed with the granulated product (5 g) including the hemihydrate, the ion-exchange capacities of this granulated product toward Na+ and K+ were 1.1–1.2 and 0.38–0.58 meq/g, respectively, showing the separation factor (αNaK) of 18–25. When artificial brackish water also flowed into the column, very small quantities of the Mg2+ and Ca2+ were adsorbed; consequently, a selective ion-exchange property of the granulated product toward K+ was recognized. Also, the carbonaceous part in the granulated product adsorbed such coloring matter as Methylene Blue.
  • Sumio Ichiba, Satoshi Oshima, Hisao Negita, Haruhiko Tanaka
    1980 Volume 53 Issue 12 Pages 3560-3562
    Published: 1980
    Released: April 19, 2006
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    Ammonium chloride tetrachlorozincate, (NH4)3Cl[ZnCl4], decomposes to ZnCl2 in two stages through an intermediate phase (NH4)2[ZnCl4]. In the first stage, 1 mol of NH4Cl is lost by one-dimensional diffusion mechanisms with the activation energy of 138 kJ mol−1, and in the second stage the release of two moles of NH4Cl is controlled by a random nucleation reaction with the activation energy of 126 kJ mol−1, corresponding to the bondbreaking. Anhydrous alkali metal tetrachlorozincate complexes, M2[ZnCl4](M=Na, K, Rb, Cs), are obtained by solid reactions with alkali chlorides when (NH4)3Cl[ZnCl4] decomposes. A dry chemical method using (NH4)3Cl[ZnCl4] as a starting material is proposed for the preparation of the anhydrous chlorozincate complexes, which have thus far been difficult to synthesize.
  • Tsutomu Shin-ike, Gin-ya Adachi, Jiro Shiokawa, Masahiko Shimada, Mits ...
    1980 Volume 53 Issue 12 Pages 3563-3566
    Published: 1980
    Released: April 19, 2006
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    The reaction of erbium sesquioxide (Er2O3) or ytterbium sesquioxide (Yb2O3) with vanadium dioxide (VO2) at 1400 °C and 50 kbar and 30 kbar pressures was studied. Quadrivalent vanadium ions were reduced to the trivalent state, erbium vanadite (ErVO3) or ytterbium vanadite (YbVO3) being obtained. The crystal structure of ErVO3 obtained at 50 kbar pressure was vaterite-type isostructural with ErBO3 belonging to a hexagonal system, and that obtained at 30 kbar calcite-type belonging to a rhombohedral (pseudo-hexagonal) system. In the reaction of Yb2O3 with VO2 at high pressure, a perovskite-type crystal was obtained. The electrical and magnetic properties of the vaterite- and the calcite-type ErVO3 were studied.
  • Masashi Goto, Kazuhiko Ikenoya, Daido Ishii
    1980 Volume 53 Issue 12 Pages 3567-3572
    Published: 1980
    Released: April 19, 2006
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    Anodic stripping semidifferential electroanalysis using a gold disk working electrode was proposed for the trace determination of mercury(II) ion, theoretical predictions being verified. A gold electrode was steeped in aqua regia, activated electrochemically before use, and rotated during the course of pre-electrolysis. A hydroxylamine hydrochloride medium was selected as supporting electrolyte. The detection limit was found to be ca. 0.5 nM under the pre-electrolysis conditions of 10 min at 0 V vs. Ag/AgCl. The relative standard deviation was ca. ±4% for the measurement at 2 nM level. Removal of the oxygen dissolved in sample solutions was not necessary. Experiments were carried out to examine the feasibility of the technique to environmental analysis. The method consists of only the following procedure: sample acidification, standard mercury(II) ion addition, UV irradiation pretreatment, and medium exchange for stripping. It was successfully applied to river water and sea water to separately evaluate ionic mercury, mercury occluded in organic matter, and total mercury (excluding mercury occluded in inorganic matter).
  • Kikuo Miyokawa, Hakaru Masuda, Isao Masuda
    1980 Volume 53 Issue 12 Pages 3573-3576
    Published: 1980
    Released: April 19, 2006
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    The thermal behavior of five complexes, [Co(NH3)6]Cl3 (1), [Co(NH3)5NO2]Cl2 (2), [Co(NH3)5NO]Cl2 (3), [(NH3)5Co–N(O)–NO–Co(NH3)5]Cl4·2H2O (4), and [(NH3)5Co–NO–ON–Co(NH3)5]Cl4·4H2O (5), has been investigated. The pyrolysis-gaschromatographic technique has been successfully applied to the N2- and N2O analyses of the gases evolved on the pyrolysis of the complexes. The thermal decomposition of these complexes is characterized predominantly by the reduction process of Co(III) to Co(II). In the simple nitrosyl 3, the NO group reduces the Co(III) ion and dissociates as NO. As for the remaining complexes, a thermally induced transient-state tends to dissociate H+ from the coordinated ammonia as follows : CoIII–NH3→[CoIII–NH2δ−···Hδ+]→CoII+NH2+H+. The NH2 species is subsequently decomposed as NH2→2/3NH3+1/6N2. Moreover, H+ is captured by an anionic species and/or the NH3 present in the system, that is, by Cl and NH3 forming NH4Cl in the case of 1, by NO2 and NH3 forming NH4NO2, which then decomposes to N2 and H2O, in 2, and by N2O22− forming H2N2O2, which then decomposes to N2O and H2O, in 4. The 5 complex undergoes an exothermic decomposition, affording a larger amount of N2 and N2O than those to be expected from the above stoichiometry, suggesting an oxidative behavior of the bridged, dimeric (–NO–ON–)2− group towards ammonia.
  • Akira Fuyuhiro, Kazuaki Yamanari, Yoichi Shimura
    1980 Volume 53 Issue 12 Pages 3577-3584
    Published: 1980
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    A four-component solubility isotherm consisting of (Λ-[Co(en)3]3+, Δ[Co(en)3]3+)–(Br,(R,R)-C4H4O62−)–H2O was determined at 25 °C. It was found that three double salts, rac-[Co(en)3]Br3·3H2O, Λ-[Co(en)3]Br(d-C4H4O6)·5H2O, and Λ-[Co(en)3]0.48·Δ-[Co(en)3]0.52(d-C4H4O6)1.5·5H2O and a gelatinous precipitate exist, six invariant points appearing. Application of this phase diagram to practical optical resolutions is discussed. The solubility of each salt in the system was measured in the range 5–65 °C in water, that of Λ and Δ-[Co(en)3](d-C4H4O6)1.5·nH2O being found to be reversed at 42 °C.
  • Katsumi Hayashi, Masanosuke Takagi
    1980 Volume 53 Issue 12 Pages 3585-3589
    Published: 1980
    Released: April 19, 2006
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    Restrictive factors of oxygen release from dispersed particles of perfluorocarbon (PFC) in a form of emulsion have been studied by polarographic reduction currents of oxygen in the emulsion. The oxygen reduction currents in PFC emulsion in open system increased linearly with the volume fraction of PFC component, and were diffusion-controlled. The increase of current was ascribed to the increase of oxygen supply to the electrode from PFC particles in the emulsion. Analyzing the oxygen reduction current due to PFC particles, the ratio of diffusion coefficients of oxygen inside and outside PFC particle (D1D0) and the oxygen partition coefficient between the both sides (C1C0) were obtained. The release of oxygen from PFC particle was rate-determined by oxygen diffusion in the particle and the diffusion itself was determined by inner viscosity of PFC particle. The surfactant layer of PFC particle did not play any appreciable role such as permeability barrier for oxygen transportation.
  • Masataka Moriyasu, Yohei Hashimoto
    1980 Volume 53 Issue 12 Pages 3590-3595
    Published: 1980
    Released: April 19, 2006
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    The equilibrium of labile ternary complex formation of metal dialkyldithiocarbamate chelates (MA2+MB2\oversetk\undersetk−\ ightleftharpoons 2MAB, K=[MAB]2/[MA2][MB2]) has been investigated by high-performance liquid chromatography, the separation process of which is so fast that kinetically unstable ternary complexes can be eluted with no disproportionation during the course of chromatography. High-performance liquid chromatography makes it possible to halt the progress of considerably fast reactions at the moment when the solution of reaction system is injected into the column. Thus, chromatograms obtained indicate the concentration of each species before chromatography, facilitating the determination of equilibrium constant K of Ni(II) and Cu(II) chelates. The equilibrium constants obtained are always 4.0, suggesting that ternary complex formation is controlled by a statistical factor. Disproportionation takes place by collision of two ternary metal chelates, the rate constants being of the order 101–102 M−1 s−1 (Ni(II) chelates) and 103 M−1 s−1 (Cu(II) chelates). The activation parameters of ternary complex formation have been obtained.
  • Akifumi Yamada, Yasuo Nakabayashi, Tadatsugu Yoshikuni, Nobuyuki Tanak ...
    1980 Volume 53 Issue 12 Pages 3596-3600
    Published: 1980
    Released: April 19, 2006
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    The polarographic reduction of hexakis(urea) chromium (III) ions at the dropping mercury electrode has been studied in various supporting electrolyte solutions. This complex exhibits two irreversible reduction waves; the first corresponds to Cr(III)→Cr(II), and the second, to Cr(II)→Cr(0). The kinetic parameters of the electrode reactions were determined in various supporting electrolyte solutions and at varied ionic strengths by means of Tast polarography. The differential-pulse polarographic characteristics of this complex are also given.
  • Takeo Ohsaka, Noboru Oyama, Hiroaki Matsuda
    1980 Volume 53 Issue 12 Pages 3601-3604
    Published: 1980
    Released: April 19, 2006
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    The formation constants of Co(II)–ethylenediamine-N-acetate (edma), –diethylenetriamine (dien) and –iminodiacetate (ida) complexes were determined by potentiometric titration in 1.0 M NaClO4 solution at 25 °C. The following results were obtained. Edma: logβ101=7.51, logβ102=14.05: dien: logβ101=9.34, logβ102=16.89; ida: logβ101=6.54, logβ102=11.95, βpqr being the overall formation constant defined in the text. The relative effects of amino and carboxyl groups on the affinity of ligands to Co(II) ion are discussed.
  • Kazuaki Yamanari, Yoichi Shimura
    1980 Volume 53 Issue 12 Pages 3605-3609
    Published: 1980
    Released: April 19, 2006
    JOURNALS FREE ACCESS
    From the reaction of (2-aminoethanethiolato)bis(ethylenediamine)cobalt(III)(2+) complex with α,ω-dibromoalkanes Br(CH2)nBr, a series of novel monobridged dinuclear cobalt(III) complexes [(en)2Co{NH2(CH2)2S(CH2)nS(CH2)2NH2}Co(en)2]6+ (n=1, 2, 3, 4, 5, 6, 8, and 10) were prepared and characterized on the basis of their absorption, circular dichroism, and infrared spectra and elemental analyses. In the case of n=2, two geometrical isomers, meso and rac, were isolated and identified.
  • Hirokazu Hara, Satoshi Okazaki, Taitiro Fujinaga
    1980 Volume 53 Issue 12 Pages 3610-3614
    Published: 1980
    Released: April 19, 2006
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    An enhancing effect of alkylphenols on the selectivity of the liquid membrane electrode responsive to organic sulfonate ion has been investigated. The interference of perchlorate ion expressed in terms of the selectivity coefficient decreased to one eighthundredth in the presence of p-t-octylphenol. This effect was attributed to the formation of the hydrogen bonding between the phenol and sulfonate. The dependence of the potentiometric behavior, paticularly with respect to the selectivity on the membrane components was examined. The optimum composition of the ion-exchanger for sulfonate was found to be 0.05 mol dm−3 trioctylmethylammonium p-toluenesulfonate with 0.5 mol dm−3 p-t-octylphenol in o-dichlorobenzene. The decrease of the selectivity coefficient for perchlorate due to the phenol was also discussed in relation to ion-exchange equilibrium constants, ionic parameters, and dissociation constants of the ion-pair. The effect of the membrane solvents was also discussed in terms of their solubility parameters.
  • Yoshio Ueno, Tadaaki Miyano, Makoto Okawara
    1980 Volume 53 Issue 12 Pages 3615-3618
    Published: 1980
    Released: April 19, 2006
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    Oxidation of the hydroxy sulfides [PhS(CH2)nCH(OH)R] with hexabutyldistannoxane (HBD)–bromine system was studied in order to clarify neighboring group participation during the course of reaction. The oxidation products were found to be highly dependent on the positions of the two functional groups [sulfide and hydroxyl group]. Thus hydroxy sulfoxides [PhSO(CH2)nCH(OH)R] were obtained as the main product when n=1 or 2, bromo sulfones [PhSO2(CH2)nCHBrR] being predominant when n=3 or 4. Keto sulfoxide [PhSO(CH2)nCOR] was exclusively formed when n=6. The results are discussed in terms of the different intramolecular interactions depending on the positions of the two functional groups.
  • Kazuhiko Tanaka, Syuichi Matsui, Aritsune Kaji
    1980 Volume 53 Issue 12 Pages 3619-3622
    Published: 1980
    Released: April 19, 2006
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    (1-Ethoxyethoxy)methyl and 1-(1-ethoxyethoxy)ethyl phenyl sulfones undergo metalation with LDA in THF in the presence of HMPA. The resulting lithium salts were easily alkylated with various alkyl halides and hydrolyzed under mild conditions to give the corresponding carbonyl compounds. The new synthetic method for the preparation of aldehydes and ketones employing these carbanions has been developed.
  • Jun Uzawa, Shoji Zushi, Yoshio Kodama, Yoshimasa Fukuda, Ken Nishihata ...
    1980 Volume 53 Issue 12 Pages 3623-3630
    Published: 1980
    Released: April 19, 2006
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    The conformation has been studied, by means of NMR spectroscopy, for diastereoisomeric pairs of a series of alcohols having the following general structure:
    CH_3CH(C_6H_5)CH(OH)–R
    where R is a methyl, ethyl, isopropyl, or a t-butyl group. It has been demonstrated that the alkyl group (R) is oriented close to the phenyl group in the most preferred conformations; this conclusion is essentially in accord with the results obtained for the structurally related sulfoxides. The general occurrence of an attractive interaction (the CH/π interaction) has, therefore, been suggested between an alkyl and a phenyl group.
  • Shoji Zushi, Yoshio Kodama, Ken Nishihata, Koshiro Umemura, Motohiro N ...
    1980 Volume 53 Issue 12 Pages 3631-3640
    Published: 1980
    Released: April 19, 2006
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    The conformations have been studied by means of NMR spectroscopy, largely by the computer simulation of the lanthanoid-induced shifts, for a series of aliphatic carbonyl compounds with the following structures: CH3CH(C6H5)CO–R; R=H, CH3, C2H5, i-C3H7, and t-C4H9. It has been suggested that two rotamers are important in the conformational equilibria of these ketones, in which the R–C–C–C6H5 dihedral angle is ca. 30° and ca. 90°. The relative stability of the above two rotamers has been found to depend on the nature of the alkyl group, R. The results have been discussed in light of the possible weak attractive forces, the CH/π and CH/n interactions.
  • Hitoshi Takeshita, Isao Kouno, Mitsuaki Iino, Hisakatsu Iwabuchi, Danj ...
    1980 Volume 53 Issue 12 Pages 3641-3647
    Published: 1980
    Released: April 19, 2006
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    Unlike ethylene, 1,1-dimethoxyethene, an electron-rich olefin, has been photocycloadded to a cis-hexahydroindenone to form a norprotoilludane derivative with a correct stereostructure. Methylation and subsequent chemical transformations yielded several oxygenated derivatives, from which the parent hydrocarbon, protoillud-7-ene, was obtained by deoxygenation. Independent evidence for the stereostructures of the synthetic derivatives has been provided by the X-ray crystallographic analysis of a dihydroxy acetal.
  • Masahiko Kato, Keizo Takatoku, Satoru Ito, Mitsuru Funakura, Toshio Mi ...
    1980 Volume 53 Issue 12 Pages 3648-3654
    Published: 1980
    Released: April 19, 2006
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    The photolysis of (1S)-exo-1-methoxycarbonylmethyl-3-t-butyl-1a,7b-dihydro-1H-cyclopropa[a]naphthalene gave (7S)-5-t-butyl-7-methoxycarbonylmethyl-7H-benzocycloheptene by a 1,5-sigmatropic shift, proving the rearrangement to proceed with the inversion of the configuration of the migrating center.
  • Tetsuo Suami, Katsumi Nakamura
    1980 Volume 53 Issue 12 Pages 3655-3657
    Published: 1980
    Released: April 19, 2006
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    In order to obtain an effective antibiotic against a resistant strain of bacteria, two hydroxyl groups on C-5 and 6″ of kanamycin B were removed. 5,6″-Dideoxykanamycin B thus prepared was subjected to antimicrobial tests, its structure being established by mass and 13C NMR spectroscopy.
  • Hiroaki Kagami, Takashi Hanzawa, Nobuo Suzuki, Shoso Yamaguchi, Masami ...
    1980 Volume 53 Issue 12 Pages 3658-3660
    Published: 1980
    Released: April 19, 2006
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    1,3- and 1,1-Disubstituted thioureas reacted with diethoxy disulfide to give carbodiimides and 1,2,4-thiadiazoles respectively. 1,1,3-Trisubstituted thioureas and diethoxy disulfide afforded trialkyl(trialkylamidino)thioureas.
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