Bulletin of the Chemical Society of Japan
Online ISSN : 1348-0634
Print ISSN : 0009-2673
ISSN-L : 0009-2673
Volume 89 , Issue 3
Showing 1-16 articles out of 16 articles from the selected issue
Accounts for Elements Science
  • Makoto Yamashita
    2016 Volume 89 Issue 3 Pages 269-281
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: November 16, 2015
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    In this article, recent developments regarding the organometallic chemistry of boron-containing pincer ligands are reviewed. Boron-based pincer ligands can be subdivided into two main classes, which are based on either diazaborole or carborane. All the papers relevant to such boron-based pincer ligands that have been published since 2009 are included in this review, which also summarizes applications of transition-metal complexes containing such boron-containing pincer ligands in catalytic and/or bond-cleavage reactions.
    This review summarizes recent developments regarding the fundamental organometallic chemistry of transition-metal complexes containing boron-containing pincer ligand and applications toward catalytic and/or bond-cleavage reactions. Fullsize Image
     
Award Accounts
The Chemical Society of Japan Award for Creative Work for 2013
  • Keiko Shimamoto
    2016 Volume 89 Issue 3 Pages 282-295
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: November 02, 2015
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    Membrane proteins, such as receptors, transporters, and enzymes, play various roles in the survival of organisms. Discovery and development of new bioactive molecules interacting with these proteins are indispensable for understanding the mechanisms of biological events. This account summarizes our efforts on (1) design and synthesis of glutamate transporter blockers to elucidate the mechanism of excitatory neurotransmission process and (2) identification of a novel glycolipid that is essential for membrane protein integration.
    Discovery and development of new bioactive molecules are indispensable for understanding the mechanisms of biological events. This account summarizes the following: (1) design and synthesis of glutamate transporter blockers and (2) identification of a novel glycolipid essential for membrane protein integration. Fullsize Image
     
The Chemical Society of Japan Award for Young Chemists for 2014
  • Izumi Iwakura, Atsushi Yabushita
    2016 Volume 89 Issue 3 Pages 296-307
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: November 02, 2015
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    Femtochemistry began from the observation of transition states (TSs) in gas-phase photoreactions. Later developments in visible ultrashort laser pulses enabled visualization of real-time changes in the molecular vibrational modes during photoreactions, including those in the liquid phase. However, TSs in thermal reactions could still not be studied, because the conventional femtosecond laser pulse cannot trigger chemical reactions in the electronic ground state. In the present work, a visible ultrashort laser pulse was used to cause an induced Raman process, whereby Raman active molecular vibrational modes were excited in the electronic ground states, which triggers the reaction induced by coherent molecular vibrational excitation in the electronic ground state just after photoexcitation. Using the “reaction by coherent molecular vibration”, we have successfully observed the TSs in a “thermal” reaction, thermal Claisen rearrangement.
    A visible ultrashort pulse laser was used to cause an induced Raman process, whereby Raman active molecular vibrational modes were excited in the electronic ground states, which trigger the reaction induced by coherent molecular vibrational excitation in the electronic ground state. Fullsize Image
     
BCSJ Award Article
  • Abraham J. P. Teunissen, Roy J. C. van der Haas, Jef A. J. M. Vekemans ...
    2016 Volume 89 Issue 3 Pages 308-314
    Published: March 15, 2016
    Released: March 15, 2016
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    Recently, our group has reported on the ureidopyrimidinone (UPy) induced buffering of 2,7-diamido-1,8-naphthyridine (NaPy) and used this phenomenon to regulate the catalysis of the Michael addition of 2,4-pentanedione to trans-β-nitrostyrene. We now show that the observed catalytic activity of NaPy is the result of a strong synergy between NaPy and trace amounts of K2CO3, resulting in a more than 100-fold increase in reaction rate compared to the two compounds separately. By keeping the concentration of K2CO3, as well as NaPy, constant, an improved regulation of the catalytic activity is achieved. We show that the catalytic activity can be precisely regulated in a noncovalent manner via the addition of the UPy motif. Finally, different salts and Michael substrates are screened to assess the selectivity of this catalytic couple and to provide a platform for future research in molecular buffering, regulation, and chemical networks.
    We report on the use of 2,7-diamido-1,8-naphthyridine as phase-transfer catalyst for the Michael addition, whose activity can be regulated in a noncovalent manner via the complementary ureidopyrimidinone motif. The influence of this finding on previously reported results is discussed. Fullsize Image
     
 
  • Keiji Kinoshita, Takashi Kawakami, Yasushi Morita, Toru Saito, Shusuke ...
    2016 Volume 89 Issue 3 Pages 315-333
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 15, 2015
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    Organic ferromagnets and advanced magneticmetals have received continued interest over many decades. The systematic investigation of open-shell radicals had been reported by Morita and co-workers. Especially, trioxotriangulene (TOT) as a pure organic radical source was expected to realize novel electrical and spin properties. Based on their experimental results, they pointed out that Br3TOT and (t-Bu)3TOT, which are two types of TOT-based crystals, have different electrical properties. In this study, we have attempted to investigate the origins of the novel properties of the two crystals from various points of view such as the shape of the TOT radicals, nature of stacking in the TOT column (sliding parallel versus antiparallel stacking), spatial interactions between neighboring pairs, various types of magnetic interactions (e.g., Jab, Ueff, and tab) between two radicals, nature of the diradical character (y and ysys) and related chemical indices (U, I), change in the binding energies with changing geometries, and electrical conductivity (i.e., IV characteristics) of Au–TOT–TOT–Au systems. Finally, it is concluded that the magnetic interactions in the column structure for the former crystal are more effectively controlled than those in the latter crystal. High electric conductivity can be expected for Br3TOT, whereas (t-Bu)3TOT is thought to be a normal antiferromagnetic insulator.
  • Siby Mathew, Fazalurahman Kuttassery, Daisuke Yamamoto, Satomi Onuki, ...
    2016 Volume 89 Issue 3 Pages 334-336
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 18, 2015
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    Water-soluble cationic 5,10,15,20-tetra(N-methyl-4′-pyridiniumyl)porphyrinatoaluminum(III) (AlTMPyP) has been synthesized by novel one-pot reaction between the parent free-base porphyrin and trimethyl aluminum in a heterogeneous system at ambient temperature. Subsequent addition of water results in the formation of hydroxy-coordinated AlTMPyP(OH) in high yield (96%).
  • Ambara R. Pradipta, Katsunori Tanaka
    2016 Volume 89 Issue 3 Pages 337-345
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 03, 2015
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    Imines are among the most ubiquitous species in organic and bioorganic chemistry; however, the reactivities of N-alkyl unsaturated imines have not been thoroughly explored due to their instability profiles. Here, we describe the novel reactivity of N-alkyl unsaturated imines derived from substituted aldehydes, a chiral aminoalcohol, and paraformaldehyde to produce hexahydropyrimidines and 1,3,5-triazacyclooctanes through a formal asymmetric [4+2] and [4+2+2] cycloaddition reaction in a stereocontrolled manner. The reaction products were successfully transformed via simple functional group manipulations to the variously substituted chiral 1,3-diamines, which could not be simply accessed by other methods.
  • Tetsu Yonezawa, Takashi Asano, Masaki Matsubara
    2016 Volume 89 Issue 3 Pages 346-353
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 04, 2015
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    The ability of surface-assisted laser desorption/ionization mass spectroscopy (SALDI-MS) of low-molecular-weight compounds using six types of commercially available TiO2 nanoparticles (NPs) was examined. In all cases, TiO2 NPs gave strong Na+-adduct sample ion peaks. Some chemicals, which rarely show proton-adduct sample ion peaks by MALDI-MS, such as aspirin and barbital, could be easily detected by using TiO2 NPs. The key factors determining the SALDI ability of TiO2 NPs are their purity, ratio of rutile, and particle size.
  • Masashi Yoshitake, Kazuya Kubo, Toru Endo, Shin-ichiro Noro, Tomoyuki ...
    2016 Volume 89 Issue 3 Pages 354-360
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 04, 2015
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    Coordination polymers based on oxalate-bridged {[MnIICrIII(oxalate)3]} complexes of (DAT-2H2+)(DCH[18]crown-6)2[MnII(CH3OH)CrIII(oxalate)3]2(CH3OH)3 and (DABCO-H+)2(DABCO-2H2+)[MnII(CH3OH)(Cl)CrIII(oxalate)3]2−2(CH3OH), where DAT, DABCO, and DCH[18]crown-6 denote 2,5-diaminotoluene, 1,4-diazabicyclo[2.2.2]octane, and cis-syn-cis-dicyclohexano[18]crown-6, respectively, were synthesized. The crystal structure of the former complex was composed of [MnII(Λ)(CH3OH)CrIII(Λ)(oxalate)3] units, whereas that of the latter crystal was composed of [MnII(Λ)(CH3OH)(Cl)CrIII(Δ)(oxalate)3]2− units. The large flexible supramolecular cation in the former provided the two-dimensional structure of [MnII(Λ)(CH3OH)CrIII(Λ)(oxalate)3], although the two-dimensional honeycomb structure of the {[MnII(Δ)CrIII(Λ)(oxalate)3]} and {[MnII(Λ)CrIII(Δ)(oxalate)3]} networks are often observed for the oxalate complexes. The round-shaped DABCO molecule in the latter induced a one-dimensional chain structure of [MnII(Λ)(CH3OH)CrIII(Δ)(oxalate)3]. The former crystal showed a magnetic field dependence of magnetization typical for a spin-canting system.
  • Shinzi Kato, Osamu Niyomura, Masahiro Ebihara, Jing-Dong Guo, Shigeru ...
    2016 Volume 89 Issue 3 Pages 361-368
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 07, 2015
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    The X-ray structure analysis of arenecarbochalcogenoic acids (ArCOEH and ArCEOH, E = S, Se, Te) is successful for 4-MeC6H4COSH for the first time, which reveals that the syn-conformer forms a planar cyclic dimer with two S–H···O=C hydrogen bonds in the solid state. Density functional theory calculations are performed for benzenecarbochalcogenoic acids (C6H5COEH and C6H5CEOH), the tetrahydrofuran (THF)-solvated acids, and the cyclic dimers of the acids. It is suggested that arenechalcogenol acids (ArCOEH) form cyclic dimers in the solid state, although Della Védova and co-workers reported that catemeric hydrogen-bonding chains are observed for the crystal structures of selenoacetic acid (MeCOSeH). Calculations demonstrate that arenecarbochalcogenoic acids exist predominantly as chalcogenoxo tautomers (ArCEOH) in polar solvents such as THF especially at low temperatures, unlike the solid-state cases, which are consistent with several experimental results.
  • Toshinao Tatsuno, Takayuki Okamoto, Tomotarou Ezaki, Toshihiro Isobe, ...
    2016 Volume 89 Issue 3 Pages 369-374
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 10, 2015
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    Due to its high sensitivity to changes in the environmental dielectric constant, localized surface plasmon resonance (LSPR) is utilized for various sensing materials. However, because of this high sensitivity, it is difficult to detect a specific substance among mixed materials. Here, we enhanced the size selectivity using a metal nanostructure. By preparing a cup-like metal nanostructure that is the same size as a virus, this cup-like structure may be able to capture a virus, and thus the LSPR characteristics would change. This phenomenon would not occur for larger materials, such as animal cells, i.e., this cup-like structure may have selectivity for material size. In this paper, we fabricated metal nanocups out of two-dimensional colloidal crystals by exploiting the difference of interfacial energy at a dielectric/metal interface. The size selectivity and plasmon characteristics of the fabricated metal nanocups were investigated with model viruses, i.e., virus-like polystyrene (PSt) nanoparticles with almost the same dielectric constant and size as a virus. As a result, the transmission spectra show a 20-nm red shift in the visible light range before and after adsorption of the model virus. Field emission scanning electron microscopy (FE-SEM), optical microscopy, UV–vis spectrometry and contact angle measurement results are also discussed.
  • In Seob Park, Masaki Numata, Chihaya Adachi, Takuma Yasuda
    2016 Volume 89 Issue 3 Pages 375-377
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 18, 2015
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    A highly efficient blue thermally activated delayed fluorescence (TADF) material based on phenazaborin and spiroacridan units was developed. A blue-emitting organic light-emitting diode containing the phenazaborin derivative as a TADF emitter exhibited a high external electroluminescence quantum efficiency of 18.2%.
  • Hideto Matsuoka, Shinichi Mizutani, Chika Watanabe, Seigo Yamauchi
    2016 Volume 89 Issue 3 Pages 378-384
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 18, 2015
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    Polymer chain morphology and its response to annealing were investigated in terms of g-tensor anisotropy in poly(3-hexylthiophene) (P3HT)/fullerene blend films fabricated by dip coating. The g-anisotropy highly resolved by W-band (94 GHz) electron paramagnetic resonance (EPR) spectroscopy enabled us to precisely determine the molecular orientation of P3HT. The substrate dependence of the morphology was also investigated by W-band EPR spectroscopy. The determined morphology and EPR line width provided insight into the growth of P3HT crystalline domains, which was correlated with solar cell performance.
  • Sho Kawakami, Atsushi Mori, Ken Nagashima, Shuichi Hashimoto, Masanobu ...
    2016 Volume 89 Issue 3 Pages 385-393
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 22, 2015
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    Aiming at fabrication of hybrid plasmonic–photonic crystals, gel-immobilized colloidal crystals made of a polystyrene colloidal suspension and an N-(hydroxymethyl)acrylamide-based gel were immersed into an aqueous dispersion of gold nanoparticles. Atomic force microscope (AFM) observations have been performed for the gel-immobilized colloidal crystals with gold nanoparticles deposited on their surfaces. In the present study, the diameter of a colloidal sphere was ca. 190 nm. The diameter of a gold nanoparticle was the same as in a preliminary study, ca. 40 nm. Various immersion times up to two hours were tested. Surface of a sample of 2 h immersion has been observed. Prior to the AFM observation, the sample was dried in a desiccator for 18 h. We have identified a face-centered cubic {111} structure of a colloidal crystal of nearly close packing. Nanoparticles isolated with one another have been observed on the surface of gel-immobilized crystal, which can be regarded as gold nanoparticles from their sizes.
  • Kazumasa Hayasaka, Kouji Kamata, Hiroshi Nakazawa
    2016 Volume 89 Issue 3 Pages 394-404
    Published: March 15, 2016
    Released: March 15, 2016
    [Advance publication] Released: December 07, 2015
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    Several iron complexes bearing an iminobipyridine ligand, (RBPIAr)FeBr2 (R = H, Me; Ar = Mes, Dipp), were synthesized. These iron complexes exhibited high catalytic activities with the help of NaBHEt3 for the hydrosilylation of 1-octene with primary, secondary, and tertiary silanes. The reaction between 1-octene and PhSiH3 produced three different species: mono- (Ph(octyl)SiH2), di- (Ph(octyl)2SiH), and trialkylated (Ph(octyl)3Si) silanes. The selective formation of Ph(octyl)SiH2 and Ph(octyl)2SiH could be achieved under different conditions. Single or double hydrosilylation reactions of secondary silanes (PhMeSiH2 and Ph2SiH2) afforded tertiary and quaternary silanes, respectively. The iron iminobipyridine complexes exhibited catalytic activity in organic solvents such as hexane, toluene, diethyl ether, and THF; an appropriate solvent choice could reverse the mono/dialkylated selectivity of the reacting silanes. In addition, a high catalyst turnover number of 12038 was achieved for the reaction between 1-octene and Ph2SiH2, and the catalyst remained active at 100 °C without any loss of activity.
  • Mohammad Abbasi, Mohammad Reza Mohammadizadeh, Zahra Moradi
    2016 Volume 89 Issue 3 Pages 405-407
    Published: March 15, 2016
    Released: March 15, 2016
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    An efficient procedure to reduce sulfoxides using ascorbic acid has been developed. Using this procedure structurally diverse sulfoxides were reduced by treating with ascorbic acid in the presence of a catalytic amount of N-bromosuccinimide (NBS) at room temperature in high yields.
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