2024/02/27 更新

写真b

スガマタ コウ
菅又 功
SUGAMATA Koh
*大学が定期的に情報更新している項目(その他は、researchmapの登録情報を転載)
所属*
理学研究科 化学専攻 博士課程前期課程
理学研究科 化学専攻 博士課程後期課程
職名*
特任准教授
学位
博士(理学) ( 2012年3月   京都大学 )
研究テーマ*
  • 有機無機材料化学・有機元素化学。環境調和型分子の開発を通じ、カーボンニュートラルな社会構築に貢献することを目標としている。非常に小さい細孔であるマイクロ孔を有する多孔性材料を活用した高効率なガス貯蔵分子の合成およびその応用を検討している。また、分子骨格への元素導入により特異な性質を有する新規有機分子の合成及びそれらの物性解析に関する研究にも取り組んでいる。

  • 学内職務経歴*
    • 2022年4月 - 現在 
      理学研究科   化学専攻 博士課程前期課程   特任准教授
    • 2022年4月 - 現在 
      理学研究科   化学専攻 博士課程後期課程   特任准教授
    • 2017年10月 - 2022年3月 
      理学部   助教
     

    研究分野

    • ナノテク・材料 / 有機機能材料

    経歴

    • 2022年4月 - 現在 
      立教大学   理学部 化学科   特任准教授

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      国名:日本国

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    • 2017年10月 - 2022年3月 
      立教大学   理学部   助教

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    学歴

    • 2009年4月 - 2012年3月 
      京都大学   理学研究科   化学専攻

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      国名: 日本国

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    論文

    • [1]Ferrocenophane Bridged by a 9-Silafluorenylidene Moiety

      Shinnosuke Usuba, Koh Sugamata, Shogo Morisako, Takahiro Sasamori

      Inorganics12 ( 3 ) 66 - 66   2024年2月22日

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      掲載種別:研究論文(学術雑誌)   出版者・発行元:MDPI AG  

      Sila[1]ferrocenophane bearing a 9-silafluorenylidene moiety (1) as a bridging unit was synthesized and isolated as a stable crystalline compound. Sila[1]ferrocenophane 1, which was newly obtained in this study, was characterized by spectroscopic analyses, a single-crystal X-ray diffraction (SC-XRD) analysis, and electrochemical measurements. Due to the characteristic 9-silafluorenyl moiety, 1 exhibited large electron affinity and a slightly higher oxidation potential relative to that of ferrocene. In addition, 1 was found to undergo ring-opening polymerization (ROP) triggered by thermolysis at a lower temperature relative to that of Ph2Sifc (1′, fc = 1,1′-ferrocenylidene). It also underwent ROP through reduction by KC8 to give the corresponding polymeric compound. The DFT calculations suggested that one-electron reduction of 1 would promote ring-opening polymerization, as shown in the experimental results.

      DOI: 10.3390/inorganics12030066

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    • Zn-Based Metal-Organic Frameworks Using Triptycene Hexacarboxylate Ligands: Synthesis, Structure, and Gas-Sorption Properties. 国際誌

      Koh Sugamata, Shoko Yamada, Daichi Yanagisawa, Natsuki Amanokura, Akihiro Shirai, Mao Minoura

      Chemistry A European Journal (Weinheim an der Bergstrasse, Germany)   e202302080   2023年8月17日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      A series of metal-organic frameworks (MOFs) based on zinc ions and two triptycene ligands of different size have been synthesized under solvothermal conditions. Structural analyses revealed that they are isostructural 3D-network MOFs. The high porosity and thermal stability of these MOFs can be attributed to the highly rigid triptycene-based ligands. Their BET specific surface areas depend on the size of the triptycene ligands. In contrast to these surface-area data, the H2 and CO2 adsorption of these MOFs is larger for MOFs with small pores. Consequently, we introduced functional groups to the bridge-head position of the triptycene ligands and investigated their effect on the gas-sorption properties. The results unveiled the role of the functional groups in the specific CO2 binding via an induced interaction between adsorbates and the functional groups. Excellent H2 and CO2 properties in these MOFs were achieved in the absence of open metal sites.

      DOI: 10.1002/chem.202302080

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    • 2-Heteraallenes. 国際誌

      Koh Sugamata, Takahiro Sasamori

      Dalton transactions (Cambridge, England : 2003)52 ( 29 ) 9882 - 9892   2023年7月25日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      While analogues of allenes with heavier main-group elements (group 14-16) have been extensively studied, 2-heteraallenes are rare chemical species whose properties are mostly unknown. It is also notable that the synthesis and isolation of allene-type molecules are not widespread, despite the extensive study of two-coordinated low-valent chemical species.

      DOI: 10.1039/d3dt01559a

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    • A Linear C=Ge=C Heteroallene with a Di-coordinated Germanium Atom. 国際誌

      Koh Sugamata, Teppei Asakawa, Daisuke Hashizume, Mao Minoura

      Angewandte Chemie (International ed. in English)62 ( 24 ) e202302836   2023年6月12日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      Allenes (>C=C=C<) are classified as cumulated dienes with a linear structure and an sp-hybridized central carbon atom. We have synthesized and isolated a stable 2-germapropadiene with bulky silyl substituents. The 2-germapropadiene allene moiety adopts a linear structure both in the solid state and in solution. An X-ray diffraction electron-density-distribution (EDD) analysis of this 2-germapropadiene confirmed the linear C=Ge=C geometry with a formally sp-hybridized germanium atom that bears two orthogonal C=Ge π-bonds. Based on detailed structural and computational studies, we concluded that the linear geometry of the isolated 2-germapropadiene most likely arises from the negative hyperconjugation of the silyl substituents at the terminal carbon atoms. The 2-germapropadiene reacts rapidly with nucleophiles, indicating that the linearly oriented germanium atom is highly electrophilic.

      DOI: 10.1002/anie.202302836

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    • Controlling the Flexibility of Carbazole-Based Metal-Organic Frameworks by Substituent Effects. 国際誌

      Koh Sugamata, Akihiro Shirai, Mao Minoura

      Chemistry A European Journal (Weinheim an der Bergstrasse, Germany)29 ( 25 ) e202203442   2023年5月2日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      We have developed highly porous Cu-based metal-organic frameworks (MOFs) using carbazole-type linkers. The novel topological structure of these MOFs was revealed by single-crystal X-ray diffraction analysis. Molecular adsorption/desorption experiments indicated that these MOFs are flexible and change their structure upon adsorption/desorption of organic solvents and gas molecules. These MOFs exhibit unprecedented properties that allow controlling their flexibility by adding a functional group onto the central benzene ring of the organic ligand. For example, the introduction of electron-donating substituents increases the robustness of the resulting MOFs. These MOFs also exhibit flexibility-dependent differences in gas-adsorption and -separation performance. Thus, this study represents the first example of controlling the flexibility of MOFs with the same topological structure via the substituent effect of functional groups introduced into the organic ligand.

      DOI: 10.1002/chem.202203442

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    • Synthesis and Structural Analysis of Organic Cyclic Polyselenides Obtained from the Reaction of a Bissilylcarbenoid with Selenium

      Koh Sugamata, Teppei Asakawa, Mao Minoura

      EUROPEAN JOURNAL OF INORGANIC CHEMISTRY26 ( 11 )   2023年4月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

      The synthesis and isolation of the first examples of a tetraselenolane and a hexaselenepane, obtained from the reaction of a bissilylcarbenoid ((R2CBrLi)-C-Si; R-Si=SiMePh2) with elemental selenium, is reported. The molecular structures of these cyclic polyselenides were determined using single-crystal X-ray diffraction analysis. The selective synthesis of these polyselenides was achieved by controlling the reaction temperature. Stoichiometric deselenation of the hexaselenepane with triphenylphosphine afforded the corresponding tetraselenolane in quantitative yield. Further deselenation of the tetraselenolane with excess triphenylphosphine did not furnish the expected selenoketone but the diselenirane, as confirmed by spectroscopic analysis.

      DOI: 10.1002/ejic.202200780

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    • Synthesis of a Dibenzo-1,6,2,5-dioxadisilocine and Its Unexpected Reductive Coupling with Phenanthrene#

      Narumi Itoh, Koh Sugamata, Shogo Morisako, Shinobu Aoyagi, Hideki Yorimitstu, Takahiro Sasamori

      CHEMISTRY LETTERS52 ( 3 ) 177 - 180   2023年3月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

      A stable dibenzo-1,6,2,5-dioxadisilocine was synthesized as a difunctional electrophile for double-silylation reactions. Its molecular structure was fully characterized by spectroscopic means and single-crystal X-ray diffraction analysis. The reductive coupling with phenanthrene using a dispersion of sodium afforded an unexpected silylated polycyclic compound via a formal [3+3] dimerization of phenanthrene skeletons.

      DOI: 10.1246/cl.220478

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    • ガス貯蔵・分離材料を指向した多孔性配位高分子の開発

      菅又 功, 白井 昭宏, 箕浦 真生

      有機合成化学協会誌81 ( 1 ) 46 - 52   2023年1月1日

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      記述言語:日本語   出版者・発行元:公益社団法人 有機合成化学協会  

      DOI: 10.5059/yukigoseikyokaishi.81.46

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    • Tellurium-Centered Bent Allenes: Synthesis, Characterization, and Reactivity. 国際誌

      Koh Sugamata, Teppei Asakawa, Yukiko Urao, Mao Minoura

      Inorganic chemistry61 ( 44 ) 17641 - 17645   2022年11月7日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      Compounds with multiple bonds between elements of the second and fifth periods are extremely unstable, and systematic investigations into their properties remain elusive. Herein, we report a tellurium-centered heteroallene that contains multiple bonds between carbon and tellurium. This compound is the first example of bis(methylene)-λ4-tellane, which was synthesized and fully characterized using multinuclear NMR spectroscopy and X-ray crystallography. In the solid state, this λ4-tellane exhibits a bent allene structure for the C═Te═C moiety and unsaturated Te-C bonds. Interestingly, the allene-type structure is retained in the solution, which is reflected in an absorption band due to the π-π* transition at 610 nm. This λ4-tellane also exhibits unique reactivity toward dihalogermylenes, which yielded rare cyclic telluragermetanes.

      DOI: 10.1021/acs.inorgchem.2c02697

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    • Gas Adsorption in R<sub>2</sub>-MOF-5 Difunctionalized with Alkyl Groups

      Koh Sugamata, Sho Kobayashi, Teruyuki Iihama, Mao Minoura

      EUROPEAN JOURNAL OF INORGANIC CHEMISTRY2021 ( 31 ) 3185 - 3190   2021年8月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

      Zinc terephthalate metal-organic framework (MOF) MOF-5 and some of its dialkylated derivatives (R-2-MOF-5; R=Me, Et, Pr, Bu) were obtained from a solvothermal synthesis using 2,5-dialkyl-1,4-benzenedicarboxylic acids with zinc nitrite. The effect of the solvent on the solvothermal synthesis of R-2-MOF-5 was investigated. For R=H and Me, interpenetrating or non-interpenetrating MOFs obtained depending on the choice of reaction solvent, while for R=Et, Pr, and Bu, no such solvent effect was observed, and only jungle-gym-type MOFs were generated. All compounds were fully characterized using powder X-ray diffraction analysis (PXRD), Fourier-transform infrared (FT-IR) spectroscopy, and thermogravimetric analysis (TGA). After activation, all these compounds exhibit significant porosity, as confirmed by N-2-, H-2-, and CO2-sorption experiments. The N-2-adsorption capacity of these compounds depends on the size of the attached alkyl groups, while the H-2-uptake values tend to increase for the alkyl-functionalized MOFs relative to the unfunctionalized parent MOFs and exhibit a maximum value for Pr-2-MOF-5.

      DOI: 10.1002/ejic.202100466

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    • PCP/MOFの水素貯蔵量向上のための有機合成的アプローチ—Approach toward Improving Hydrogen Storage of PCP/MOF Using Synthetic Organic Chemistry—特集 社会実装のステージを迎えた水素貯蔵技術

      菅又 功, 白井 昭宏, 箕浦 真生

      水素エネルギーシステム = Journal of the Hydrogen Energy Systems Society of Japan / 水素エネルギー協会 編46 ( 4 ) 263 - 268   2021年

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      記述言語:日本語   出版者・発行元:水素エネルギー協会  

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    • Structural analysis of interpenetrated methyl-modified MOF-5 and its gas-adsorption properties. 国際誌

      Koh Sugamata, Daichi Yanagisawa, Keiko Awano, Teruyuki Iihama, Mao Minoura

      Acta crystallographica. Section C, Structural chemistry76 ( Pt 9 ) 845 - 849   2020年9月1日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      The first example of an interpenetrated methyl-modified MOF-5 with the formula Zn4O(DMBDC)3(DMF)2, where DMBDC2- is 2,5-dimethylbenzene-1,4-dicarboxylate and DMF is N,N-dimethylformamide (henceforth denoted as Me2MOF-5-int), namely, poly[tris(μ4-2,5-dimethylbenzene-1,4-dicarboxylato)bis(N,N-dimethylformamide)-μ4-oxido-tetrazinc(II)], [Zn4(C10H8O4)3O(C3H7NO)2]n, has been obtained from a solvothermal synthesis of 2,5-dimethylbenzene-1,4-dicarboxylic acid and Zn(NO3)2·6H2O in DMF. A systematic study revealed that the choice of solvent is of critical importance for the synthesis of phase-pure Me2MOF-5-int, which was thoroughly characterized by single-crystal and powder X-ray diffraction (PXRD), as well as by gas-adsorption analyses. The Brunauer-Emmett-Teller surface area of Me2MOF-5-int (660 m2 g-1), determined by N2 adsorption, is much lower than that of nonpenetrated Me2MOF-5 (2420 m2 g-1). However, Me2MOF-5-int displays an H2 uptake capacity of 1.26 wt% at 77 K and 1.0 bar, which is comparable to that of non-interpenetrated Me2MOF-5 (1.51 wt%).

      DOI: 10.1107/S2053229620010177

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    • Structural analysis of and selective CO2 adsorption in mixed-ligand hydroxamate-based metal-organic frameworks. 国際誌

      Koh Sugamata, Chikaze Takagi, Keiko Awano, Teruyuki Iihama, Mao Minoura

      Dalton transactions (Cambridge, England : 2003)49 ( 29 ) 9948 - 9952   2020年8月7日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      Two mixed-ligand metal-organic frameworks, [Zn2(BDHA)0.5(INA)3] (MOF-1: H2BDHA = benzene-1,4-dihydroxamic acid; HINA = isonicotinic acid) and [Co2(BDHA)0.5(INA)3(DMF)] (MOF-2), were solvothermally synthesized and fully characterized by single-crystal X-ray crystallography as well as N2, H2, and CO2 gas-sorption measurements. The results constitute the first detailed analysis of the bonding environment around the hydroxamates in such MOFs, which are simultaneously decorated with Lewis-basic sites from the hydroxamate moieties and metal sites predisposed for coordinative unsaturation. MOF-2 shows a desirably selective adsorption of CO2 relative to N2.

      DOI: 10.1039/d0dt01105c

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    • (Thio)(silyl)carbene and (seleno)(silyl)carbene gold(i) complexes from the reaction of bis(methylene)-λ<SUP>4</SUP>-sulfane and bis(methylene)-λ<SUP>4</SUP>-selane with chloro(dimethylsulfide)gold(i)

      Koh Sugamata, Yukiko Urao, Mao Minoura

      DALTON TRANSACTIONS49 ( 23 ) 7688 - 7691   2020年6月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ROYAL SOC CHEMISTRY  

      The dinuclear (thio)(silyl)carbene and (seleno)(silyl)carbene gold(i) complexes1and2were obtained from the reaction of two equivalents of AuCl(SMe2) with the stable bis(methylene)-lambda(4)-chalcogenanes3and4, respectively. The reaction proceeds under elimination of the chlorosilane moiety of3and4. Complexes1and2were characterized by spectroscopic and X-ray diffraction (XRD) analyses. The(13)C NMR signals for the carbene centers of 1 (309 ppm) and 2 (345 ppm) are by more than 150 ppm downfield shifted relative to those for other known (NHC)AuCl complexes. These results indicate that (chalcogeno)(silyl)carbenes, like (amino)(silyl)carbenes, belong to the push-spectator family of carbenes.

      DOI: 10.1039/d0dt00967a

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    • Synthesis, Structure, and Reactivity of a Thermally Stable Dialkylgermylene

      Fumiaki Suzuki, Ryohei Nishino, Mariko Yukimoto, Koh Sugamata, Mao Minoura

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN93 ( 2 ) 249 - 251   2020年2月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

      The dialkylgermylene Trp*Ge-2: (Trp*: peripherally extended sterically demanding alkyl groups based on the triptycyl (Trp) framework), was obtained from the reaction of Trp*Li with GeCl2 center dot dioxane. The structure of Trp*Ge-2: was unequivocally determined by NMR and UV-vis spectroscopy, mass spectrometry, and a single-crystal X-ray diffraction analysis. Moreover, the reactivity of Trp*Ge-2: was examined.

      DOI: 10.1246/bcsj.20190338

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    • A stable bis(methylene)-λ<SUP>4</SUP>-selane with a >CSeC< bond containing Se(iv)

      K. Sugamata, Y. Urao, M. Minoura

      CHEMICAL COMMUNICATIONS55 ( 57 ) 8254 - 8257   2019年7月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:ROYAL SOC CHEMISTRY  

      Bis(methylene)-lambda(4)-selane 1, which represents a new class of heteroallenes, was synthesized and isolated as a stable purple crystalline solid. X-ray crystallographic analysis revealed a bent allene-type structure with pseudo C-2v symmetry and a bent CSeC moiety that contains a 3-center-4-electron pi-bond. The NMR spectrum of 1 shows compelling evidence for a slow rotation of the SeC moieties at room temperature. The Se-77 NMR spectrum of 1 contains one signal in the region characteristic for Se(iv) compounds.

      DOI: 10.1039/c9cc04121d

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    • Systematic Synthesis and Crystal Structures of Tetraaryltellurium Compounds Ar<sub>4</sub>Te<SUP>IV</SUP>

      Sho Kobayashi, Koh Sugamata, Mao Minoura

      BULLETIN OF THE CHEMICAL SOCIETY OF JAPAN92 ( 3 ) 661 - 663   2019年3月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

      Hypervalent tetraaryltellurium(IV) compounds of the type Ar4TeIV (1: Ar = C6H5; 2: Ar = p-H3CC6H4; 3: Ar = p-t-BuC6H4; 4: Ar = p-F3CC6H4) were prepared via a convenient one-pot reaction between the isolated corresponding ArLi reagent and TeCl4. X-ray crystallographic analyses of 1-4 revealed distortedpseudo-trigonal-bipyramidal (TBP) structures for Ar 4 Te and the TBP character was analyzed by the dihedral angle method.

      DOI: 10.1246/bcsj.20180380

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    • Synthesis of Ferrocenyl-Substituted Organochalcogenyldichlorogermanes

      Takahiro Sasamori, Yuko Suzuki, Koh Sugamata, Tomohiro Sugahara, Norihiro Tokitoh

      INORGANICS6 ( 3 )   2018年9月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:MDPI  

      Reaction of the isolable ferrocenyldichlorogermyl anion, Fc*GeCl2- (Fc* = 2,5-bis(3,5-di-t-butylphenyl)-1-ferrocenyl), with the isolable chalcogenenyl halides resulted in the formation of the corresponding organochalcogenyldichlorogermanes that were structurally characterized. Thus, it was demonstrated the use of sterically demanding ferrocenyl groups allowed isolating stable crystalline organochalcogenyldichlorogermanes.

      DOI: 10.3390/inorganics6030068

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    • Group 2 metal bis(arenecarbochalcogenoate)(crown ether) complexes: isolation and structural analysis. 国際誌

      Yoshiharu Tatematsu, Shinzi Kato, Norio Nakata, Masahiro Ebihara, Osamu Niyomura, Koh Sugamata, Mariko Yukimoto, Mao Minoura

      Dalton transactions (Cambridge, England : 2003)47 ( 29 ) 9787 - 9794   2018年7月24日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      A series of Group 2 metal bis(arenecarbochalcogenoato)(crown ether) complexes M(EE'CAr)2(L)(L')x (M = Mg, Ca, Sr, Ba; Ar = aryl; E = S, Se; E' = O, S; L = H2O or THF; L' = 15-crown-5, 18-crown-6) were synthesized and their structures were revealed by X-ray analyses. The two carbothioato ligands in Mg, Ca and Sr 15-crown-5 complexes are located on the same side of the crown ether plane, while those in Mg, Ca, Sr, and Ba 18-crown-6 compounds are on both sides of the 18-crown-6 plane (trans relative to the plane). For the Ca 15-crown-5 complex, both carbothioato ligands are connected to the central Ca ion through an oxygen atom in a monodentate manner, and the two hydrogen atoms of the coordinated water molecule are intramolecularly hydrogen-bonded with thiocarbonyl sulfur atoms. One of the two carbothioate groups in the Ca 18-crown-6 complex is connected in a bidentate manner to the central metal, while the other is connected in a monodentate manner through an oxygen atom. The two thiocarboxylato ligands in the Sr 15-crown-5 congener are connected in a bidentate fashion to the same side of the crown ether plane. The Ca and Sr compounds are the first examples of alkali earth metal carbochalcogenoate complexes in which carbochalcogenolato ligands are connected in a monodentate manner through an oxygen atom. Both chalcogenoato ligands in Ba(SOCC6H4Me-4)2(18-crown-6) and Sr(SeOCC6H4Me-4)2(18-crown-6) are coordinated in a bidentate manner to the central metal ion.

      DOI: 10.1039/c8dt01959b

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    • Synthesis and Structure of a Stable Bis(methylene)-λ4 -sulfane. 国際誌

      Koh Sugamata, Daisuke Hashizume, Yuko Suzuki, Takahiro Sasamori, Shigeru Ishii

      Chemistry (Weinheim an der Bergstrasse, Germany)24 ( 27 ) 6922 - 6926   2018年5月11日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      Bis(methylene)-λ4 -sulfane 1, a >C=S=C< heterocumulene, was obtained as a red crystalline solid from the reaction between elemental sulfur and a carbenoid that contains sterically demanding silylalkyl groups. Under atmospheric conditions, and even at elevated temperatures, 1 exhibits extraordinary stability. The molecular structure and electron-density distribution of 1 were analyzed by single-crystal X-ray diffraction analysis, which revealed a bent C=S=C geometry with C=S=C π-bonds. These results, combined with those of variable-temperature NMR measurements and theoretical calculations suggest a slow rotation of the S=C moieties in 1, the stability and structure of which were further examined by theoretical calculations.

      DOI: 10.1002/chem.201800828

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    • Synthesis of a Peripherally Extended Triptycyl Group as an Aliphatic Steric Protection Group and Its Application to the Kinetic Stabilization of an Aliphatic Sulfenic Acid

      Mariko Yukimoto, Ryohei Nishino, Fumiaki Suzuki, Michihiro Ishihara, Koh Sugamata, Mao Minoura

      CHEMISTRY LETTERS47 ( 4 ) 425 - 428   2018年4月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

      Trp*, a novel triptycene (Trp)-based aliphatic steric protection group was synthesized, and its potential to offer kinetic stabilization by steric protection was evaluated in the context of synthesizing a sulfenic acid (RSOH), i.e., a highly reactive sulfur-containing species. The isolated sulfenic acid Trp* SOH is thermally very stable, which clearly demonstrates the steric protection provided by Trp*.

      DOI: 10.1246/cl.171230

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    • Synthesis, Structure, and Thermolysis of Tris(dimethylphenylsilyl)methyl Sulfenyl Chloride

      Koh Sugamata, Shigeru Ishii

      CHEMISTRY LETTERS46 ( 6 ) 837 - 839   2017年6月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

      Sulfenyl chlorides, i.e., di-coordinated sulfur(II) chlorides are useful precursors for a variety of organic sulfur compounds. Herein, the synthesis, structure, and reactivity of a sulfenyl chloride that bears a bulky tris(dimethylphenylsilyl) methyl group on the sulfur atom are reported. The thermolysis of this sulfenyl chloride resulted in the generation of the corresponding bissilylthioketone via the 1,2-elimination of chlorodimethyl-phenylsilane.

      DOI: 10.1246/cl.170188

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    • Selenium-Substituted Phosphaalkenes Obtained through 1,2-Elimination of Chlorosilanes from Selenenylchlorophosphines

      Takahiro Sasamori, Jose Manuel Villalba Franco, Jing-Dong Guo, Koh Sugamata, Shigeru Nagase, Rainer Streubel, Norihiro Tokitoh

      EUROPEAN JOURNAL OF INORGANIC CHEMISTRY ( 5 ) 678 - 684   2016年2月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

      Stable selenenyl-chlorophosphines, bearing a silylalkyl group, were synthesized. Subsequent treatment with Lewis acids such as AlCl3 afforded the corresponding phospha-alkenes. A reaction mechanism that proceeds through an intramolecular 1,2-elimination of chlorosilane was proposed.

      DOI: 10.1002/ejic.201500989

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    • Reaction of a diaryldigermyne with ethylene. 国際誌

      Takahiro Sasamori, Tomohiro Sugahara, Tomohiro Agou, Koh Sugamata, Jing-Dong Guo, Shigeru Nagase, Norihiro Tokitoh

      Chemical science6 ( 10 ) 5526 - 5530   2015年10月1日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      Reaction of the stable digermyne BbtGe[triple bond, length as m-dash]GeBbt (Bbt = 2,6-[CH(SiMe3)2]2-4-[C(SiMe3)3]-C6H2) with ethylene initially afforded the corresponding 1,2-digermacyclobutene. Depending on the reaction conditions applied, further reaction of this 1,2-digermacyclobutene with ethylene furnished two different reaction products: a 1,4-digermabicyclo[2.2.0]hexane or a bis(germiranyl)ethane. Combined experimental and theoretical results suggested that the 1,4-digermabicyclo[2.2.0]hexane and the bis(germiranyl)ethane are the thermodynamic and kinetic reaction products, respectively. A reaction mechanism in agreement with these results was proposed.

      DOI: 10.1039/c5sc01266j

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    • Kinetically Stabilized Organophosphorus Radicals

      Koh Sugamata

      JOURNAL OF SYNTHETIC ORGANIC CHEMISTRY JAPAN73 ( 3 ) 276 - 277   2015年3月

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      記述言語:日本語   出版者・発行元:SOC SYNTHETIC ORGANIC CHEM JPN  

      The organophosphorus radicals have drawn much attention in organic chemistry, biological processes, and functional materials due to their high reactivity Although various species of organophosphorus radicals in solution have been observed by EPR spectroscopy, only a few examples have been isolated in the solid state. By using suitable bulky substituents, isolation of organophosphorus radicals such as dialkylphosphinyl radical, triarylphosphine radical cation, and tetraaryldiphosphine radical cation were achieved. The EPR spectra of those radicals showed the spin density of their radicals are mainly localized on phosphorus atom.

      DOI: 10.5059/yukigoseikyokaishi.73.276

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    • 速度論的に安定化された有機リンラジカル種

      菅又 功

      有機合成化学協会誌73 ( 3 ) 276 - 277   2015年

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      記述言語:日本語   出版者・発行元:公益社団法人 有機合成化学協会  

      DOI: 10.5059/yukigoseikyokaishi.73.276

      CiNii Article

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    • ChemInform Abstract: Unique Synthetic Approach Toward a Phosphaalkene: Synthesis of a Selenium-Substituted Phosphaalkene with Bulky Substituents. 査読有り

      Koh Sugamata, Takahiro Sasamori, Norihiro Tokitoh

      ChemInform45 ( 32 ) no   2014年7月

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      出版者・発行元:Wiley  

      DOI: 10.1002/chin.201432205

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    • Unique Synthetic Approach toward a Phosphaalkene: Synthesis of a Selenium-substituted Phosphaalkene with Bulky Substituents

      Koh Sugamata, Takahiro Sasamori, Norihiro Tokitoh

      CHEMISTRY LETTERS43 ( 1 ) 95 - 96   2014年1月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:CHEMICAL SOC JAPAN  

      A selenium-substituted phosphaalkene, (Me3Si)(2)C=PSeTrp (1, Trp: 9-triptycyl), was synthesized by two methods, substitution reaction of (Me3Si)(2)C=PCl (3) with TrpSeLi, and treatment of TsiP(Cl)SeTrp (4, Tsi: C(SiMe3)(3)) with a catalytic amount of AlCl3. The newly, obtained phosphaalkene was characterized in detail.

      DOI: 10.1246/cl.130862

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    • Generation of an Organotellurium(II) Cation

      Koh Sugamata, Takahiro Sasamori, Norihiro Tokitoh

      EUROPEAN JOURNAL OF INORGANIC CHEMISTRY ( 5 ) 775 - 778   2012年2月

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-V C H VERLAG GMBH  

      We expected that the chemical trapping products of low-coordinated tellurenyl cation species can also be kinetically stabilized by the Tbt or Bbt group. Recently, we have reported the halogenation reactions of Bbt-substituted ditelluride, BbtTeTeBbt, leading to the formation of the Te-II-Te-IV mixed-valent tellurenyl fluoride, BbtTeTe(F)(2)Bbt, and tellurenyl halides, BbtTeX (X = Cl, Br, I). During the dehalogenation reactions of these tellurium halides, it is rational to postulate the formation of a tellurenyl cation species as an intermediate. In this paper, we report the successful trapping of tellurenyl cation species with butadienes or triphenylphosphane, and the regeneration of the tellurenyl cation species by thermal retro [1+4] cycloaddition of the diene adducts.

      DOI: 10.1002/ejic.201101313

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    • Fluorination reaction of a ditelluride bearing bulky aryl substituents: formation of mixed-valent Te(IV)-Te(II) ditelluride difluoride. 国際誌

      Koh Sugamata, Takahiro Sasamori, Norihiro Tokitoh

      Chemistry, an Asian journal6 ( 9 ) 2301 - 3   2011年9月5日

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      記述言語:英語   掲載種別:研究論文(学術雑誌)  

      DOI: 10.1002/asia.201100368

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    • Halogenation Reactions of a Ditelluride Having Bulky Aryl Groups Leading to the Formation of Organotellurium Halides

      Takahiro Sasamori, Koh Sugamata, Norihiro Tokitoh

      HETEROATOM CHEMISTRY22 ( 3-4 ) 405 - 411   2011年

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      記述言語:英語   掲載種別:研究論文(学術雑誌)   出版者・発行元:WILEY-BLACKWELL  

      Halogenation reactions of BbtTe-TeBbt (Bbt; 2,6-bis[bis(trimethylsilyl)methyl]-4-[tris (trimethylsilyl)methyl]phenyl) with SO2Cl2, Br-2, and I-2 were examined. When 1 equiv of the reagents were used, the corresponding tellurium monohalides were obtained as stable crystalline compounds. Although iodination reaction of BbtTe-TeBbt using 3 equiv of I-2 afforded BbtTeI, treatment of BbtTe-TeBbt with 3 equiv of SO2Cl2 and Br-2 gave the corresponding tellurium trthalides, BbtTeX(3)(X = Cl, Br), as stable crystalline compounds. Characterization of the obtained tellurium mono- and trihalides was achieved by the spectroscopic and crystallographic analyses, together with theoretical calculations. (C) 2011 Wiley Periodicals, Inc. Heteroatom Chem 22:405-411, 2011; View this article online at wileyonlinelibrary.com. DOI 10.1002/hc.20698

      DOI: 10.1002/hc.20698

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    ▼全件表示

    共同研究・競争的資金等の研究

    • 高周期典型元素を中心とするヘテロアレン型分子の創製と系統的物性解明

      日本学術振興会  科学研究費助成事業 

      菅又 功

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      2020年4月 - 2023年3月

      課題番号:20K05468

      配分額:4290000円 ( 直接経費:3300000円 、 間接経費:990000円 )

      カルベン等価体である、シリル置換カルベノイド(Ph2MeSi)2CLiBrを活用して、一連の高周期典型元素を中心とするヘテロアレン類縁体>C=E=C<を合成単離し、これらの特異なベント型累積二重結合に起因する特異な性質を明らかとすることを目的とする。アレン(R2C=C=CR2)は、置換基や配位子により中心炭素の酸化状態が変化し、異なる性質を発現することから近年盛んに研究が行われている。ごく最近、申請者らが合成に成功している、高周期16族元素の硫黄およびセレンを中心とするヘテロアレン型分子ビス(メチレン)スルファンおよびセラン(>C=Ch=C<, Ch = S, Se)の特異な構造や性質を鑑み、一連の元素特性を反映したユニークな物性発現を指向して、一連の高周期典型元素を中心とするアレン型分子の創製研究を遂行する。
      令和3年度は、ビス(メチレン)カルコゲナンの系統的な性質解明を行う目的で、テルルを中心とするビス(メチレン)テランの合成・単離を行った。シリル置換カルベノイドとテルル粉末を低温で反応させ、後処理を速やかに行うことで目的のビス(メチレン)テラン(>C=Te=C<)の合成・単離に成功した。その炭素-テルル間の結合は多重結合性を有しており、その多重結合性に起因した青緑色を呈していた。ビス(メチレン)カルコゲナンの系統的性質解明のため、種々の試薬との反応を行った。2価ゲルマニウム試薬であるジクロロゲルミレンジオキサン錯体との反応では、セレン、テルル誘導体において反応が進行し、対応する4員環化合物カルコゲナゲルメタンが得られた。カルコゲン中心のベントアレンに特有の反応を見出すことに成功した。

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    • 多置換複素環形成を目指した新規ヘテロクムレン類の開発

      日本学術振興会  科学研究費助成事業 

      菅又 功

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      2018年4月 - 2020年3月

      課題番号:18K14204

      配分額:4160000円 ( 直接経費:3200000円 、 間接経費:960000円 )

      高周期16族元素である硫黄やセレンを中心とするヘテロアレン類、ビス(メチレン)-λ4-カルコゲナンはこれまでに安定な化合物として合成・単離された例はなかった。最近、研究代表者らはそれらを安定な化合物として合成・単離することに成功し、その構造や性質を明らかとした。本研究課題ではそれらの反応性調査を検討し、ビス(メチレン)セランと塩化水素、ハロゲン化試剤との反応において1,3-付加型の生成物を定量的に与えることを明らかにした。また塩化金(I)ジメチルスルフィド錯体との反応では硫黄、セレン類縁体ともに特異な反応を起こし、それぞれ対応するカルベン金(I)錯体が得られた。

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