Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 78 , Issue 1
Showing 1-21 articles out of 21 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2002
  • Takeji Hashimoto
    2005 Volume 78 Issue 1 Pages 1-39
    Published: 2005
    Released: January 13, 2005
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    We have presented studies of the mechanics of molecular assembly for multicomponent molecular systems in the context of nonlinear and nonequilibrium phenomena. The studies cover the following three themes: (i) elucidation of space-time self-assembly of hierarchical structures, in the length scale ranging from nm to μm, of binary molecular mixtures via phase transition by means of real-time and in-situ analyses with various scattering methods and microscopy methods; (ii) elucidation of self-assembly of molecular mixtures under shear flow in the context of open nonequilibrium phenomena by means of newly developed rheo-optical methods, leading us to discover new dissipative structures as well as shear-induced phase transitions both from single-phase to two-phase and from two-phase to single-phase; (iii) elucidation of the influences of chemical bonds between different component polymers in block copolymers on microphase transition and ordered microdomain structures with nano-scale periodicity and various space-group symmetries and exploration of nano-fabrication methods of microdomain structures as templates in the context of nano-science and nano-technology of block copolymers. In each of the three themes, we highlight and emphasize the fact that polymer systems provide very good model systems for basic studies of nonlinear and nonequilibrium phenomena because of the fact that large structures evolve very slowly in polymer systems. The studies may give perspectives for creating advanced soft materials responsive to environmental stimuli and for understanding activities, adaptation, and evolution of living organisms.
The Chemical Society of Japan Award for 2003
  • Seiji Shinkai, Masayuki Takeuchi
    2005 Volume 78 Issue 1 Pages 40-51
    Published: 2005
    Released: January 13, 2005
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    Sugar recognition in an aqueous system has been achieved using a boronic acid–diol interaction. Combination with an intramolecular amino group has enabled us to read out the binding process as a change in the fluorescence intensity. This novel sugar-sensing method has been combined with a concept of “molecular machinery”, providing a new guest-binding mode with allosteric functions. When this method is combined with a concept of “molecular imprinting”, it becomes possible to design sugar-selective receptors created by a combinatorial method. The sugar recognition event is useful as a trigger to control molecular assemblies such as micelles, membranes, vesicles, and gels.
The Chemical Society of Japan Award for Creative Work for 2003
  • Haruyuki Makio, Terunori Fujita
    2005 Volume 78 Issue 1 Pages 52-66
    Published: 2005
    Released: January 13, 2005
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    Olefin polymerizations with group 4 transition metal complexes having two phenoxy–imine ligands (FI Catalysts) are reviewed with an emphasis on the characteristics and mechanisms of propene polymerization. The structures and properties of FI Catalysts can be easily modified by changing phenoxy–imine ligand structures. Such catalysts can be synthesized straightforwardly from readily available chemicals. An enormous library of FI Catalysts can be built up by combining a group 4 metal center and a variety of cocatalysts. The diversified library makes FI Catalysts so versatile that polyolefins with desired properties (molecular weight, molecular weight distribution, chain-end structure, tacticity, and so on) can be obtained sometimes predictably, by selecting the appropriate combination of ligand, metal, and cocatalyst. In propene polymerization, it remains a challenge to control the stereo- and regiochemistry of monomer enchainment in order to obtain commercially valuable products. FI Catalysts can produce syndiotactic and isotactic polypropene by Ti–FI catalysts/MAO and Zr– and Hf–FI catalysts/iBu3Al/Ph3CB(C6F5)4, respectively. Because of the well-defined and tunable nature of the catalysts, the coordination environment around the metal center can be controlled by the ligand structures to achieve extremely high stereoregularities, comparable to those of heterogeneous Ziegler–Natta catalysts and metallocene catalysts. These syndio- and isospecific FI Catalysts have contrasting reaction mechanisms, i.e., the syndiospecific polymerization is mediated via 2,1-insertion under chain-end control, while isospecificity arises from 1,2-insertion and a site control mechanism. The observed syndiospecificity can originate from the inherent fluxionality of FI Catalysts between configurational isomers.
BCSJ Award Article
  • Hiroharu Suzuki, Takeaki Kakigano, Ken-ichi Tada, Minoru Igarashi, Kou ...
    2005 Volume 78 Issue 1 Pages 67-87
    Published: 2005
    Released: January 13, 2005
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    Cationic triruthenium hexahydrido complexes, [{Ru(C5Me5)}3(μ-H)6](Y) (Y = BF4, CF3SO3, 1/2(SO4), C6H5CO2, CH3CO2), have been synthesized by the reaction of diruthenium tetrahydride [{Ru(C5Me5)}2(μ-H)4] with the corresponding acid, HBF4, CF3CO2H, H2SO4, C6H5CO2H, and CH3CO2H. The trimeric structure of these complexes has been confirmed by a crystallographic study of [{Ru(C5Me5)}3(μ-H)6](PF6). The treatment of [{Ru(C5Me5)}3(μ-H)6](Y) with CH3ONa in methanol selectively afforded a neutral trinuclear pentahydrido complex, [{Ru(C5Me5)}3(μ-H)33-H)2], which underwent an intermolecular H/D exchange reaction with benzene-d6, toluene-d8, or o-xylene-d10 to give [{Ru(C5Me5)}3(μ-D)33-D)2] as the result of arene C–H bond activation via an η2-arene intermediate complex. A cationic hydrido complex, [{Ru(C5Me5)}3(μ-H)6](Y), having a carboxylate as a counter anion was equilibrated with [{Ru(C5Me5)}3(μ-H)33-H)2] in solution, and the equilibrium constant depended on the counter anion. An X-ray diffraction study showed that [{Ru(C5Me5)}3(μ-H)33-H)2] has a triangular reaction field surrounded by three C5Me5 ligands. The reaction of [{Ru(C5Me5)}3(μ-H)33-H)2] with 1 equiv of O2 proceeded with the retention of the Ru3 framework to yield an 80/20 mixture of a mono-μ3-oxo complex [{Ru(C5Me5)}3(μ-H)33-O)] and a di-μ3-oxo complex [{Ru(C5Me5)}3(μ-H)33-O)2]. A novel trinuclear μ3-iodo-tetra-μ-hydrido complex, [{Ru(C5Me5)}33-H)(μ-H)33-I)] was formed upon the treatment of [{Ru(C5Me5)}3(μ-H)33-H)2] with 1 equiv of CH3I in tetrahydrofuran. The treatment of [{Ru(C5Me5)}3(μ-H)33-H)2] with carbon monoxide generated a paramagnetic trinuclear tetracarbonyl complex, [{Ru(C5Me5)}3(μ-CO)33-CO)].
Articles
  • Hiroshi Matsuura, Tamio Tanikawa, Shuichi Ushiba, Makoto Ogawa
    2005 Volume 78 Issue 1 Pages 88-94
    Published: 2005
    Released: January 13, 2005
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    This study reports on the structure and stability of an alcohol-based polymer, which stores hydrogen in the form of ions. The hydrogen-storing polymer is produced from alcohol using a plasma-induced method. Measurements of the electrical resistivity and the IR spectra of the polymer indicate that it is in an electrically unstable state. The hydrogen produced by the polymer following the application of an electric signal demonstrates that the hydrogen ions are trapped within the polymer. The development of hydrogen-storing techniques in the form of ions improves the controllable extraction of hydrogen.
  • Sadayuki Himeno, Masayo Takamoto, Ryoko Santo, Akio Ichimura
    2005 Volume 78 Issue 1 Pages 95-100
    Published: 2005
    Released: January 13, 2005
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    For Keggin-type polyoxometalate complexes (α-[XMo12O40]n (X = S, P, As, Si, Ge; n = 2–4) and α-[XW12O40]n (X = S, P, As, Si, Ge, B, Al; n = 2–5)), the conversion processes of the first two one-electron waves into a two-electron wave were investigated in dipolar aprotic solvents containing H+, Li+, or Na+ as a Lewis acid. A simulation of the cyclic voltammogram indicated that the potential difference (ΔEmid) between the first one- and two-electron redox waves served as a useful criterion for the basicity of the Keggin anions. According to the ΔEmid values, the Keggin anions were classified into the following four groups: (1) [SW12O40]2−; (2) [SMo12O40]2−, [XW12O40]3− (X = P, As); (3) [XMo12O40]3− (X = P, As), [XW12O40]4− (X = Si, Ge); (4) [XMo12O40]4− (X = Si, Ge), [XW12O40]5− (X = B, Al). The voltammetric properties of the Keggin anions were systematized with reference to their basicities.
  • Shigeru Takagi, Hiroyuki Furuta, Toshitaka Yagi, Hiroyuki Yamada
    2005 Volume 78 Issue 1 Pages 101-106
    Published: 2005
    Released: January 13, 2005
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    A new metal–metal bonded porphyrin [(hbtbpp)In–Mn(CO)5], where hbtbpp is the dianion of 2,3,7,8,12,13,17-heptabromo-5,10,15,20-tetrakis(3,5-di-t-butylphenyl)porphyrin, has been synthesized. In our attempt to synthesize the indium complex of octabromo porphyrin using the DMF method, we found that Br atom loss occurred in the process of metal insertion. When having synthesized the metal–metal bonded porphyrin by using a mixture of (heptabromoporphyrinato)indium and (octabromoporphyrinato)indium as the starting material, only heptabromo M–M bonded porphyrin was obtained. A large ring deformation of octabromo porphyrin disturbed the formation of the M–M bond. This heptabromo M–M porphyrin has shown high stability against electroreduction or photo-irradiation.
  • Yanbei Zhu, Akihide Itoh, Hiroki Haraguchi
    2005 Volume 78 Issue 1 Pages 107-115
    Published: 2005
    Released: January 13, 2005
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    A chelating resin-packed minicolumn was developed to pretreat seawater samples for the determination of trace metals by inductively coupled plasma mass spectrometry (ICP-MS). The preconcentration conditions, such as the flow rate of sample loading, pH for adsorption, amount of ammonium acetate for eliminating matrix elements, and the amount of nitric acid for eluting trace metals from the resin, were investigated and optimized. Firstly, 50 mL of seawater samples was adjusted to pH 6.0 and loaded into the column at the flow rate of 3 mL min−1. Secondly, 8 mL of 1 M ammonium acetate and 5 mL of pure water were passed through the column for eliminating matrix elements, such as Mg and Ca. Finally, trace metals were eluted with 2.25 mL of 2 M nitric acid, and then 0.25 mL of internal standard elements (Ge, In, Re, Tl, 100 μg L−1 each) was added to the eluted solution in order to correct matrix effects in the ICP-MS measurements. The recoveries for 23 elements (Mn, Co, Ni, Cu, Zn, Y, Cd, all-REEs, Pb, and U) were more than 80%. The analytical results for the concentrations of trace metals in seawater reference material (NASS-5) agreed well with certified or reference values. The present method was also applied to the multielement analysis of the coastal seawater samples from the Take Island (Gamagoori, Aichi prefecture, Japan) and the Ise Bay (Nagoya, Aichi prefecture, Japan).
  • Syuhei Yamaguchi, Akinori Kumagai, Shigenori Nagatomo, Teizo Kitagawa, ...
    2005 Volume 78 Issue 1 Pages 116-124
    Published: 2005
    Released: January 13, 2005
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    In order to understand the effect of an oxygen-containing ligand on the physico-chemical properties and reactivities of hydrogenperoxocopper complexes, new copper(II) complexes with the N3O-type tripodal ligand bearing pivalamido groups, N,N-bis(6-pivalamido-2-pyridylmethyl)glycine (Hbpga), and N,N-bis(6-pivalamido-2-pyridylmethyl)-β-alanine (Hbpaa), have been designed and synthesized. Copper(II) complexes without any external ligand and those with a monodentate ligand, such as azido and chloro, have been prepared and characterized with the aid of electronic absorption and ESR spectroscopic, cyclic voltammetric, and X-ray structure analytical methods. The redox potential values of the Cu(II) complexes, when they were compared with the Cu(II) complex of bis(6-pivalamido-2-pyridylmethyl)(2-pyridylmethyl)amine (bppa), reported previously, shifted toward the negative side upon the introduction of a carboxylate group in the place of one pyridine of bppa. Reactions of [Cu(bpga)]ClO4 (1a) and [Cu(bpaa)]PF6 (2a) with hydrogen peroxide in the presence of triethylamine in both MeCN and MeOH solutions gave mononuclear copper(II) complexes with hydrogenperoxide(1−), Cu–bpga–OOH (1d) and Cu–bpaa–OOH (2d) systems, respectively. The intense absorption bands, assignable to LMCT (HOO → Cu(II)) and d–d bands, and ESR and resonance Raman spectra have revealed that they form trigonal bipyramidal copper complexes with OOH in an end-on fashion. The thermal stabilities of 1d and 2d have also been studied by following the reduction rate of the LMCT bands at 283 K. Those of copper(II) complexes with hydrogenperoxide(1−) have been reduced in the order 1d > 2d >> [Cu(bppa)(OOH)]+ (3d), all of which are rather stable compared with that of Cu(II)–tpa–OOH (tpa = tris(2-pyridylmethyl)amine). These findings indicate that the hydrogenperoxocopper(II) complexes are activated by introducing carboxylate coordination, although they are stabilized by hydrogen-bonding interactions.
  • Eiji Kinoshita, Kouhei Ishikawa, Emiko Kinoshita-Kikuta, Kazuhiro Ohta ...
    2005 Volume 78 Issue 1 Pages 125-131
    Published: 2005
    Released: January 13, 2005
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    A novel dinuclear zinc(II) hexaazacryptate (Zn2L3+) has been synthesized as a phosphate capture molecule in aqueous solution (L = an alkoxide form of 4,16-(2-hydroxypropano)-1,4,7,13,16,19-hexaazacyclotetracosane). Potentiometric pH titration study disclosed a 1:1 phenyl phosphate complexation with Zn2L3+. The dissociation constant, Kd ( = [Zn2L3+][PhOPO32−]/[Zn2L3+PhOPO32−]) is a small value of 6 × 10 − 7 M at 35 °C with I = 0.10 (NaNO3). The X-ray crystal analysis of the p-nitrophenyl phosphate complex with Zn2L3+ showed that the phosphate dianion binds as a bridging ligand to the two zinc(II) ions. The analogous 1:1 CH3COO-bound Zn2L3+ complex was isolated and characterized by X-ray analysis.
  • Keiko Aoki, Yumi Takeuchi, Yutaka Amao
    2005 Volume 78 Issue 1 Pages 132-134
    Published: 2005
    Released: January 13, 2005
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    Mg chlorophyll-a (MgChl-a) with imidazole-4-acetic acid (Im) as the axial ligand (MgChl-a–Im), adsorbed on a nanocrystalline TiO2 film electrode, was prepared. Further, the photoelectrical properties of a solar cell using visible-light sensitisation of the nanocrystalline TiO2 film through an axial Im ligand of MgChl-a were investigated.
  • Ruiqin Yang, Yilu Fu, Yi Zhang, Bolian Xu, Noritatsu Tsubaki
    2005 Volume 78 Issue 1 Pages 135-137
    Published: 2005
    Released: January 13, 2005
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    In-situ DRIFTS was used to clarify the reaction mechanism of a new methanol synthesis method on a Cu/ZnO catalyst at low temperature from syngas containing CO2 using an ethanol promoter. The formate species was formed by exposing Cu/ZnO catalyst to syngas, and it reacted easily with ethanol to form an ethyl formate species at low temperature. Ethyl formate was easily reduced to form methanol.
  • Xiaojun Hu, Huijie Shi, Xianfa Shi, Zhongliang Zhu, Qiuhong Sun, Yong ...
    2005 Volume 78 Issue 1 Pages 138-141
    Published: 2005
    Released: January 13, 2005
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    The selective dinitro-substituted derivative of thiacalix[4]arene was synthesized by a three-step route and characterized. Its acid–base properties in a water solution were studied by UV–vis spectroscopy. Its four pKa values were determined by Target Testing Factor Analysis (TTFA).
  • Takahisa Motomura, Hideko Nakamura, Michinori Suginome, Masahiro Murak ...
    2005 Volume 78 Issue 1 Pages 142-146
    Published: 2005
    Released: January 13, 2005
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    Oligo(naphthalene-2,3-diyl)s are synthesized by the palladium-catalyzed cross-coupling reactions of 2-naphthylzinc compounds with 2-bromonaphthalene derivatives. An NMR analysis together with an X-ray diffraction study supports the conjecture that the helical secondary structure is a common feature of the assemblies in which naphthalene-like aromatic units are linked together between the β-positions in series.
  • Mio Matsuoka, Mustanir, Soe Than, Masaaki Mishima
    2005 Volume 78 Issue 1 Pages 147-153
    Published: 2005
    Released: January 13, 2005
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    The gas phase acidities of meta- and para-substituted phenylacetylenes and benzyl alcohols were determined by measuring equilibrium constants of proton transfer reactions using a FT-ICR spectrometer. The gas phase acidities of phenylacetylenes and benzyl alcohols are related linearly to those of benzoic acids with a slope of unity. Since the CH2 group of benzyl alcohol prevents a direct π-electron interaction between substituents and the negative charge at the oxygen atom, the existence of these linear relationships suggests that σo parameters best describe the substituent effects in all three systems. Indeed, the acidities of phenylacetylenes and benzoic acids correlate with σo values determined in the gas phase. The theoretical calculations of these acidities at MP2/6-311++G**//B3LYP/6-311++G** level of theory could reproduce the substituent effects observed experimentally. The optimized geometries and the elctrostatic charges computed using the CHELPG scheme of Breneman for the conjugate anions of all three acid systems also indicate that there is no π-delocalization of the negative charge into the benzene ring.
  • Jean-Yves Kazock, Cécile Enguehard-Gueiffier, Isabelle Th&eacut ...
    2005 Volume 78 Issue 1 Pages 154-159
    Published: 2005
    Released: January 13, 2005
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    The purpose of this work was to complete a general study that we initiated on the influence of a 2-substitution on the reactivity of 8-haloimidazo[1,2-a]pyridines towards a Suzuki cross-coupling reaction, using conventional reactants in order to obtain easily performed (hetero)arylation methods with a high degree of flexibility with regard to functional groups.
  • Mohamed S. Mohamed Ahmed, Akitoshi Sekiguchi, Kentaro Masui, Atsunori ...
    2005 Volume 78 Issue 1 Pages 160-168
    Published: 2005
    Released: January 13, 2005
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    Sonogashira coupling, which is a coupling reaction of terminal alkynes with organic halides, takes place with dilute aqueous ammonia as an activator. The reaction of several terminal alkynes and aryl iodides in the presence of small excess of aqueous ammonia at room temperature furnishes the cross-coupling product in good-to-excellent yields. A water-soluble amine with a high boiling point is alternatively employed for reactions at higher temperatures. A related coupling reaction in the presence of carbon monoxide also proceeded at room temperature and under ambient pressure to afford α,β-alkynyl ketones efficiently.
  • Shigehisa Akine, Kei Goto, Takayuki Kawashima
    2005 Volume 78 Issue 1 Pages 169-179
    Published: 2005
    Released: January 13, 2005
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    The quinone-bridged calix[6]arenes 1 and 2, carrying a 1,4-benzoquinone moiety in the cavity of a calixarene macrocycle, were synthesized from the corresponding p-methoxyphenol derivatives. X-ray crystallography revealed the structures of 1 and 2, in which the quinone moiety is located inside the cone-shaped calix[6]arene framework and surrounded by the lower-rim substituents. Their 1H NMR spectra showed upfield shifts of the protons on the bridging unit in comparison with reference compounds without the calixarene framework, in accordance with their crystal structures. The cyclic voltammograms of 1 and 2 showed two waves, the second ones being considerably broadened. Their reduction potentials were found to be negatively shifted in comparison with those of the reference compounds. These shifts were explained in terms of the nonbonded interaction between the ether oxygen atoms of the calixarene moiety and the quinone moiety, as well as the sterically restricted access of the counter cation to the semiquinone anion radical. Reactions of 1 with hydroxylamine and phenylhydrazine afforded the corresponding hydroquinone along with the quinone monoimine derivatives, indicating that electron transfer from the amines proceeds quickly, although the negatively shifted reduction potentials of 1 are apparently unfavorable for the electron transfer process.
  • Kyoko Tsuji, Naoyuki Nishimura, Xuan-Ming Duan, Shuji Okada, Hidetoshi ...
    2005 Volume 78 Issue 1 Pages 180-186
    Published: 2005
    Released: January 13, 2005
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    This study synthesized a series of methoxystilbazolium analogues with π-conjugation extended by attaching a fused aromatic ring, i.e., 6-styrylisoquinolinium and 4-[2-(2-naphthyl)ethenyl]pyridinium derivatives with methoxy substituents. We evaluated their transition energies (Eegs) and second-order hyperpolarizabilities (βs) experimentally using their absorption spectra and a hyper-Rayleigh scattering measurement, respectively. Subsequently, we calculated βs using the MOPAC PM3 method. These values were compared with those of 4-[4-(4-methoxyphenyl)-1,3-butadienyl]pyridinium derivative, which is a stilbazolium analogue with π-conjugation that is simply extended by an increase of the double-bond number between two aromatic rings. This study clarified that the fused-ring systems possess large βs, irrespective of their relatively short absorption wavelengths, compared to the double-bond elongation system.
  • Takahiro Gunji, Mitsuo Unno, Koji Arimitsu, Yoshimoto Abe, Nick Long, ...
    2005 Volume 78 Issue 1 Pages 187-191
    Published: 2005
    Released: January 13, 2005
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    Homogeneous YBa2Cu3O7−δ (YBCO) and Bi2SrCa2Cu2O8+y (BSCCO) precursors were prepared by the reaction of triethanolamine with ethyl acetoacetato complexes of Y, Ba, and Cu and those of Bi, Sr, Ca, and Cu, respectively. These precursors showed melt-spinnability and converted to ceramics on heating with the elimination and combustion of organic groups. Superconductive thin films were prepared by depositing a solution on a substrate by spin-coating, followed by calcination. Epitaxial growth of the YBCO phase, with c axis normal to the substrate, was observed. The critical temperature was 88.7 K and the critical current density at 77 K and 0 T was 5 × 105 A/cm2. On the other hand, the epitaxial growth of the c axis aligned BSCCO phase was observed: the critical temperature was 77 K and the critical current density at 5 K was 6 × 104 A/cm2.
  • Aritomo Yamaguchi, Takamitsu Hayashi, Kenichi Oyaizu, Makoto Yuasa
    2005 Volume 78 Issue 1 Pages 192-194
    Published: 2005
    Released: January 13, 2005
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    The catalytic activities and structural changes of Pd containing mesoporous silica (Pd/MCM-41) catalysts for the NO + CO reaction were investigated. Pd/MCM-41 after calcination in air showed a very high catalytic activity for the NO + CO reaction because Pd metal particles with an appropriate size for the reaction were formed by the reaction gases.
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