Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 87 , Issue 4
Showing 1-17 articles out of 17 articles from the selected issue
Award Accounts
The Chemical Society of Japan Award for 2011
  • Toshiro Takao, Hiroharu Suzuki
    2014 Volume 87 Issue 4 Pages 443-458
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: December 11, 2013
    JOURNALS FREE ACCESS
    We explored polyhydrido cluster reaction chemistry for over two decades, developing rational syntheses of di-, tri-, tetra-, and pentanuclear clusters of ruthenium. In our study of cluster chemistry, we found that triruthenium pentahydrido complex [{Cp*Ru(µ-H)}33-H)2] (1) (Cp*: η5-C5Me5) reacts with linear alkanes to exclusively afford a closo-ruthenacyclopentadiene complex 2. The reaction mechanism has been elucidated by the isolation and alternative preparation of several important intermediates by the reaction of 1 with other hydrocarbons, such as alkynes, dienes, and alkenes. The mechanism is shown to consist of two reversible and four irreversible steps involving dihydrogen elimination, where the cooperative interaction of neighboring metal centers with hydrocarbons on the cluster is clearly seen. Facile migration of a hydride from a metal center to the carbon atom is also observed during the reaction, which emphasizes the crucial role of hydrido ligands in the skeletal rearrangement of hydrocarbyl ligands on a polyhydrido cluster. In addition, coupling reaction between two hydrocarbyl ligands placed on each face of the triruthenium core with concomitant partial cleavage of the cluster skeleton has also been observed. Such a flexible cluster skeleton enables unusual transformation of hydrocarbons on the cluster.
    The reaction mechanisms of triruthenium pentahydrido complex with linear alkanes leading to the exclusive formation of closo-ruthenacyclopentadiene complexes are established. In each step, the cooperative interaction of neighboring metal centers with substrates is clearly recognized. Fullsize Image
     
BCSJ Award Article
  • Takashi Shibahara, Keisuke Kawamoto, Akihiko Matsuura, Hideaki Takagi, ...
    2014 Volume 87 Issue 4 Pages 459-469
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 16, 2014
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    The reaction of sulfur-bridged incomplete cubane-type molybdenum complex [Mo3(µ-S)33-S)(dtp)3(CH3CN)(µ-OAc)] (1) (dtp: diethyl dithiophosphate) with dimethyl acetylenedicarboxylate (H3COOCC≡CCOOCH3, DMAD) in several kinds of solvents gave solvent-dependent adducts. The use of acetone, acetaldehyde, acetylacetone, ethyl acetoacetate, and acetophenone as reaction solvents gave the following adducts, respectively: [Mo3{µ-SCH(COCH3)}(µ3-S){µ3-SC(CO2CH3)=C(CO2CH3)S}(dtp)3(µ-OAc)] (2), [Mo3{µ-SCH(CHO)}(µ3-S){µ3-SC(CO2CH3)=C(CO2CH3)S}(dtp)3(µ-OAc)] (3), [Mo3{µ-SC(COCH3)(COCH3)}(µ3-S){µ3-SC(CO2CH3)=C(CO2CH3)S}(dtp)3(µ-OAc)] (4) (and [Mo3{µ-SC(COCH3)(COCH3)}(µ3-S){µ3-SC(CO2CH3)=C(CO2CH3)S}(dtp)2(acac)(µ-OAc)] (4′)), [Mo3{µ-SC(COCH3)(COOC2H5)}(µ3-S){µ3-SC(CO2CH3)=C(CO2CH3)S}(dtp)3(µ-OAc)] (5), and [Mo3{µ-SCH(COC6H5)}(µ3-S){µ3-SC(CO2CH3)=C(CO2CH3)S}(dtp)3(µ-OAc)] (6). X-ray crystallography and 1H NMR spectroscopy have revealed that in all six cases, the solvent adduct-formation resulted in the removal of two hydrogen atoms from the methyl (or methylene) group of the solvent used and in the formation of a carbon–sulfur bond; it also revealed that in some cases (2, 3, 4′, and 6) additional carbon–molybdenum bond formations occurred. Mass spectroscopy indicates that the presence of DMAD is indispensable in the two-hydrogen elimination reaction. Electronic spectra of 2, 3, and 6 have absorption bands in the visible and near-infrared region, and those of the two complexes 4 and 5 have significantly larger absorption bands in the longer wavelength region than the former group. The complex 4′, where one of the three dtp ligands is replaced by an acetylacetone anion also has a larger peak in the longer wavelength region, but the intensity is between those of the former and the latter groups. All six complexes show a chemically reversible one-electron-oxidation process corresponding to a V, IV, IV/IV, IV, IV couple and the oxidation products of these six complexes are stable under a time scale in CV measurements. The reduction processes of 2, 3, and 6 are chemically irreversible; those of 4, 4′, and 5 are reversible, and the processes correspond to a IV, IV, IV/IV, IV, III couple. A mechanism for the formation of the doubly-dehydrogenated species is suggested.
    The reaction of 1 with DMAD in acetone gave an acetone adduct 2, where two hydrogen atoms have been removed from one of the two methyl groups of the acetone in conjunction with the formation of carbon–sulfur and carbon–molybdenum bonds. Fullsize Image
     
 
  • Motohiro Banno, Ayumi Kotani, Kaoru Ohta, Keisuke Tominaga
    2014 Volume 87 Issue 4 Pages 470-478
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 29, 2014
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    The vibrational energy relaxation of the CN stretching mode of benzonitrile (BN) in solution has been investigated by infrared (IR) pump–probe spectroscopy. The peak wavenumber, line shape, and cross section of the ground state absorption band due to the CN stretching mode depend on the solvent and concentration. From the experimental results of IR spectroscopy and calculations with density functional theory, the structures of solute–solute or solute–solvent complexes are suggested. In hexane, BN exists as a monomer or a dimer in which the two CN groups are arranged antiparallel. In ethanol (EtOH), it is suggested that BN forms the antiparallel dimer and a BN–EtOH hydrogen-bonded complex. In dimethyl sulfoxide (DMSO), BN probably forms a solute–solvent complex. From the results of IR pump–probe spectroscopy, the decay time constant of the pump–probe signal shows a probe wavenumber dependence in hexane and DMSO, which indicates inhomogeneity of the microscopic environment around BN in these solvents. In EtOH, the wavenumber dependence was not observed. This suggests that the VER processes for the BN dimer and the BN–EtOH complex are accelerated from that for the monomer, and the VER times are almost identical among the two structures.
  • Kiyohiko Tabayashi, Osamu Takahashi
    2014 Volume 87 Issue 4 Pages 479-490
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 27, 2014
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    Substituent dependence of geometries and binding energies calculated for a number of carboxylic acid dimers with R-substituents using 2nd-order Møller–Plesset perturbation theory and Gaussian 4 level quantum mechanical method, is analyzed to characterize intrinsic substituent effects. Charge distribution and charge-transfer interaction of reaction centers are examined to evaluate π-electron delocalization and individual H-bond structures using natural bond orbital analysis. For (RCOOH)2 homodimers, parametric substituent-treatment by Taft and Topsom revealed that π-donor substitution increases the π-electron delocalization of conjugated C=O/C–O frames of carboxylic acids and cooperatively stabilizes the equivalent H-bonds depending on the potentiality |σR+| of π-resonance effect, i.e., substituent-enhanced RAHBs (resonance-assisted H-bonds). In contrast, π-accepting substituents are found actually inactive in these electron deficient C=O/C–O fields yielding the minimum available RAHBs similar to the reference (HCOOH)2. In (R1–COOH)(R2–COOH) heterodimers, the π-accepting substituent can only be activated under the presence of π-donor potentiality from the counter molecule, generating a cooperative substituent push–pull interaction through the corresponding H-bond. Out of two H-bonds generated, one is significantly strengthened while the other being quenched due to the substituent effects in the opposite direction. The intermolecular electron push–pull interaction is quantitatively interpreted in terms of the charge-transfer of each H-bond influenced by the π-resonance substituent effects.
  • Bholanath Mandal, Douglas J. Klein
    2014 Volume 87 Issue 4 Pages 491-497
    Published: April 15, 2014
    Released: April 15, 2014
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    Graphs of linear chains and/or cycles with homogeneous and/or alternant vertex weights have been considered. If one puts weight(s) on the terminal vertex (vertices) or edge(s) of such linear chains, another set of linear chains might result. All such vertex- or edge-weighted graphs of linear chains and cycles represent conjugated systems with heteroatom(s). Characteristic polynomial followed by trigonometric identity has been shown to be used for obtaining eigenspectra for such systems of linear chains and cycles in closed analytical forms. The analytical expressions so obtained for such systems can be used for deriving the eigenspectra of some complicated π-conjugated molecules in analytical forms.
  • Hiroki Yasuhara, Masashi Kaneko, Kazuki Koga, Tetsuya Tahara, Satoru N ...
    2014 Volume 87 Issue 4 Pages 498-505
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 31, 2014
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    The reaction rate of [(PPh3)(MeCN)Ru(µ255-C10H8)(µ-MeSSMe)Ru(MeCN)(PPh3)](BF4)2 (2A), the intermediate of oxidative addition of disulfide to produce bis(thiolato)-bridged complex [(PPh3)Ru(µ255-C10H8)(µ2-SMe)2Ru(PPh3)](BF4)2 (2), changed depending on the solvent (CDCl3, CD2Cl2, CD3COCD3, and CD3NO2). The dependency is well explained by the stabilization energy of solvation of eliminated nitrile during the reaction. The corresponding PhCN complexes [(PhCN)2(PPh3)Ru(µ255-C10H8)Ru(PPh3)(PhCN)2](BF4)2 (1C) and [(PPh3)(PhCN)Ru(µ255-C10H8)(µ-MeSSMe)Ru(PhCN)(PPh3)](BF4)2 (2C) were newly synthesized to know the effect of nitrile. The intermediate of oxidative addition of diselenide [(PPh3)(MeCN)Ru(µ255-C10H8)(µ-MeSeSeMe)Ru(MeCN)(PPh3)](BF4)2 (3A) and the corresponding end product [(PPh3)Ru(µ255-C10H8)(µ2-SeMe)2Ru(PPh3)](BF4)2 (3) were also isolated, and the structures were determined by single-crystal X-ray structural analysis.
  • Ibadur Rahman Siddiqui, Sanjay Yadav, Shayna Shamim, Shireen, Malik A ...
    2014 Volume 87 Issue 4 Pages 506-510
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 22, 2014
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    Solid-supported, microwave-assisted efficient one-pot route to N-ribonucleosides of 2-thiohydantoin via reaction of ribosylthiourea and arylglyoxal has been developed. The strategy involves initial nucleophilic addition of ribosylthiourea on arylglyoxal which on subsequent intramolecular cyclocondensation produce thiohydantoin N-ribonucleoside. The protocol involves acidic Al2O3 as solid support and was accomplished efficiently with quantitative conversion of reactants into product.
  • Shin-ichi Takekuma, Atsuki Seki, Toshie Minematsu
    2014 Volume 87 Issue 4 Pages 511-527
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 28, 2014
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    Reaction of 4-[(E)-2-(3-guaiazulenyl)diazenyl]benzene-1-carbaldehyde with guaiazulene (=7-isopropyl-1,4-dimethylazulene) in methanol in the presence of 65% hexafluorophosphoric acid at 25 °C for 2 h gives the title new monocarbenium ion compound with an equivalent of HPF6, in 97% isolated yield, which upon reduction with NaBH4 in a mixed solvent of ethanol and acetonitrile at 25 °C for 30 min affords the corresponding new H-reduction product, {4-[(E)-2-(3-guaiazulenyl)diazenyl]phenyl}(3-guaiazulenyl)methane, in 93% isolated yield. Along with the above basic studies, the difference between the delocalized π-electron system (i.e., the formation of the resonance structures) of the title compound, possessing an (E)-diazene linkage (–N=N–), and that of the structurally related new compound, possessing an (E)-ethene linkage (–CH=CH–), i.e., {4-[(E)-2-(3-guaiazulenyl)ethenyl]phenyl}(3-guaiazulenyl)methylium hexafluorophosphate, is reported in detail.
  • Tadatsugu Yamaguchi, Yusuke Kamihashi, Toru Ozeki, Ayaka Uyama, Jun-ic ...
    2014 Volume 87 Issue 4 Pages 528-538
    Published: April 15, 2014
    Released: April 15, 2014
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    Three types of diarylethenes having one phenol moiety as an aromatic unit were synthesized in order to control pH change upon irradiation with UV and visible light. Upon irradiation with 313 nm light, these open-ring isomers were transformed to thermally unstable colored isomers in methanol solution. During the storage of the photoirradiated diarylethene solutions in the dark for 10 min, the thermally unstable closed-ring isomers were converted to thermally stable keto isomers. The structures of these isomers were characterized by 1H NMR and X-ray crystallography. The keto isomers were transformed to the initial phenol isomer upon irradiation with visible light. Additionally, we also found the formation of a novel photochromic diarylethene derivative having one keto group on the cyclopentane ring during UV irradiation. A pH change between the two isomers was observed in a mixture of ethanol and water.
  • Masayuki Yamashita, Nobuyuki Negoro, Tsuneo Yasuma, Toru Yamano
    2014 Volume 87 Issue 4 Pages 539-543
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: February 04, 2014
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    A preparation via Rh-catalyzed asymmetric hydrogenation has been developed for (2,3-dihydrobenzofuran-3-yl)acetic acid derivatives, a key intermediate in the synthesis of the active pharmaceutical ingredient for GPR40 agonist, fasiglifam. Use of a cationic rhodium–Et-FerroTANE complex yielded the desired product in high enantiomeric excess (91%) and quantitative yield, and was thus recommended for further process development.
  • Ichiro Hayakawa, Shuya Shioda, Akiyuki Ikedo, Hideo Kigoshi
    2014 Volume 87 Issue 4 Pages 544-549
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 31, 2014
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    Glaziovianin A and its O7-propargyl analogue are potent cytotoxic isoflavones. We found that the O7-propargyl analogue completely arrested cell-cycle progression. We have achieved the large-scale synthesis of glaziovianin A and its O7-propargyl analogue for further in vivo experimentation.
  • Akihiro Nomoto, Satoko Hayashi, Takuya Fujiyama, Takuma Ikeda, Kiichi ...
    2014 Volume 87 Issue 4 Pages 550-552
    Published: April 15, 2014
    Released: April 15, 2014
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    Upon photoirradiation, diphenyl diselenide and diphenyl ditelluride reacted with ethynylferrocene to afford the corresponding bischalcogenated vinylferrocenes. Regio- and stereoselectivities were determined by X-ray crystal analysis, and redox properties were investigated by cyclic voltammetry.
  • Masa-aki Wakita
    2014 Volume 87 Issue 4 Pages 553-555
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: February 04, 2014
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    Polymeric lipid membranes of N-octadecylchitosan were covalently immobilized on porous supports and applied as adsorbents for purification of proteins. In addition to lipopolysaccharide, DNA was removed to its detection limit from albumin solution with a quantitative recovery of protein. Selective removal of lipopolysaccharide from IgG solution was also confirmed.
  • Hirokazu Masai, Yusuke Hino, Takayuki Yanagida, Yutaka Fujimoto, Toshi ...
    2014 Volume 87 Issue 4 Pages 556-563
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 29, 2014
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    The photoluminescence (PL) properties of rare earth (RE)-doped SnO–ZnO–P2O5 (RE-SZP) glass were examined in the visible region. RE-SZP glass, except for those doped with Ce3+, exhibited similar optical band edges because of the s–p transition in Sn2+. The RE3+ PL excitation bands in RE-SZP glass were red-shifted compared to the bands in Sn-free glass because of the energy transfer from the Sn2+ center. In addition, the emission intensity in a few RE-SZP glass systems was remarkably enhanced by Sn2+ addition. Emission decays of Sn2+ in the glass were typically independent of the RE3+, and suggest the exchange interaction between Sn2+ and RE3+. This indicated that the RE3+ cation is generally located close to the Sn2+ center in order to allow energy transfer.
  • Hirofumi Kondo, Ken-ichi Iimura
    2014 Volume 87 Issue 4 Pages 564-569
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 28, 2014
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    Partially fluorinated carboxylic acid derivatives were synthesized and their macroscopic frictions and wetting properties were examined. The carboxylic acid adsorbs on a Co–15 wt % Ni metal surface with high orientation, but the ester has a weak interaction and its film is isotropic, which are suggested by the surface energy and the FTIR measurements of the film. The outermost part of the acid is occupied by fluorinated alkyl groups and the surface energy is 10 mJ m−2, which agrees with values for the fluorinated self-assembled monolayers. The friction coefficient does not depend on the fluorine content in the lubricant molecules, not only for the highly oriented layer, but also for the isotropic film. This seems to be caused by the anchoring effect. Macroscopic friction is largely dependent on the polar group. The alkyl chains in the monolayer of the semifluorinated materials contain gauche conformers, and the odd–even effect was insignificant in the film. The molecules of the odd CH2 units in the monolayer are more inclined on average and the friction and surface energy are slightly greater than the even ones.
  • Kazuyuki Maeda, Masato Otsu, Hiroki Kobayashi, Atsushi Kondo
    2014 Volume 87 Issue 4 Pages 570-572
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: January 22, 2014
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    Inorganic–organic hybrid materials composed of [O3P–C6H4–SiO3] units and zirconium hydrothermally prepared in the presence of cationic surfactant showed nanoporosity and considerably high specific surface area.
  • Kyoso Masuda, Hideki Matsune, Sakae Takenaka, Masahiro Kishida
    2014 Volume 87 Issue 4 Pages 573-575
    Published: April 15, 2014
    Released: April 15, 2014
    [Advance publication] Released: February 03, 2014
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    Silica-coated AgCl nanoparticles are successfully prepared in an aqueous solution. AgCl nanoparticles are synthesized using poly(vinylpyrrolidone) as a protecting agent, and a silica layer is formed by hydrolysis and polycondensation of (3-aminopropyl)triethoxysilane (APTS) and tetraethoxysilane. The results explain that APTS is a key material for the formation of the silica layer in the aqueous solution system.
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