SEINO Hidetake

写真a

Affiliation

Faculty of Education and Human Studies  Department of School Education  Department of Primary and Secondary Education  Course for Primary and Secondary Education

Laboratory Address

Room 214, 3rd Bld., Faculty of Education and Human Studies

Mail Address

E-mail address

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Research Interests 【 display / non-display 】

  • Organometallic chemistry

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Graduating School 【 display / non-display 】

  • 1988.04
    -
    1992.03

    The University of Tokyo   Faculty of Engineering   Department of Industrial Chemistry   Graduated

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Graduate School 【 display / non-display 】

  • 1994.04
    -
    1997.03

    The University of Tokyo  Graduate School, Division of Engineering  Department of Chemistry and Biotechnology  Doctor's Course  Completed

  • 1992.04
    -
    1994.03

    The University of Tokyo  Graduate School, Division of Engineering  Department of Synthetic Chemistry  Master's Course  Completed

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Degree 【 display / non-display 】

  • The University of Tokyo -  Doctor (Engineering)

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Campus Career 【 display / non-display 】

  • 2025.04
    -
    Now

    Akita University   Faculty of Education and Human Studies   Department of School Education   Department of Primary and Secondary Education   Course for Primary and Secondary Education   Associate Professor  

  • 2014.04
    -
    2025.03

    Akita University   Faculty of Education and Human Studies   Department of School Education   Combined Courses for English,Mathematics and Science Teachers   Course for Science and Mathematics Teachers   Associate Professor  

  • 2013.04
    -
    2014.03

    Akita University   Faculty of Education and Human Studies   Program in Environmental and Mathematical Science   Program in Environmental and Mathematical Science   Program in Environmental and Mathematical Science   Associate Professor  

  • 2016.04
    -
    Now

    Akita University   Graduate School of Engineering Science   Part time Lecturer  

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Academic Society Affiliations 【 display / non-display 】

  • 2012.09
    -
    Now
     

    Japan

     

    The Society of Polymer Science, Japan

  • 2011.06
    -
    Now
     

    Japan

     

    Japan Society of Coordination Chemistry

  • 2011.05
    -
    Now
     

    United States

     

    American Chemical Society

  • 2005.01
    -
    Now
     

    Japan

     

    The Kinki Chemical Society, Japan

  • 2001.08
    -
    Now
     

    Japan

     

    Catalysis Society of Japan

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Research Areas 【 display / non-display 】

  • Nanotechnology/Materials / Inorganic/coordination chemistry

  • Nanotechnology/Materials / Synthetic organic chemistry

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Research Career 【 display / non-display 】

  • Catalytic reactions modeling functions of metalloenzymes

    Grant-in-Aid for Scientific Research  

    Periods of research：

    2004.04
    -
    Now

    Classification of research form：Individual

  • Activation of N2 molecule by transition metal-sulfide clusters

    Grant-in-Aid for Scientific Research  

    Periods of research：

    2001.04
    -
    Now

    Classification of research form：Collaboration with an Organization

  • Conversion of small molecules by using low-valent early transition metal complexes containing polydentate phosphine ligands

    Grant-in-Aid for Scientific Research  

    Periods of research：

    1998.04
    -
    Now

    Classification of research form：Individual

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Thesis for a degree 【 display / non-display 】

  • Synthesis of Organo-Nitrogen Compounds from Molecular Dinitrogen

    Hidetake Seino 

      1997.03

    Single author

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Research Achievements 【 display / non-display 】

    ◆Original paper【 display / non-display 】

  • An Iodido-Bridged Dimer of Cubane-Type RuIr3S4 Cluster: Structural Rearrangement to New Octanuclear Core and Catalytic Reduction of Hydrazine

    Hidetake Seino, Keiichi Hirata, Yusuke Arai] Risa Jojo, Masaaki Okazaki

    European Journal of Inorganic Chemistry   2000 ( 15-16 ) 1483 - 1489   2019.12  [Refereed]  [Invited]

    Research paper (journal)   Domestic Co-author

    窒素固定酵素の活性部位に存在する金属−硫黄クラスターは、立方体型のM4S3C骨格が２つ融合した構造を有する。本研究では、立方体型のRuIr3S4クラスターの二量体を合成し、それを還元することによって２つの立方体骨格が融合したRu2Ir6S8八核クラスターに誘導されることを見いだした。また、RuIr3S4クラスターの二量体がヒドラジンの還元的N−N切断反応において、高活性な触媒となることを明らかにした。

    DOI

  • Reversible Hydride Transfer to N,N'‑Diarylimidazolinium Cations from Hydrogen Catalyzed by Transition Metal Complexes Mimicking the Reaction of [Fe]-Hydrogenase

    Masahiro Hatazawa, Naoko Yoshie, and Hidetake Seino

    Inorganic Chemistry   56 ( 14 ) 8087 - 8099   2017.06  [Refereed]

    Research paper (journal)   Domestic Co-author

    [Fe]-ヒドロゲナーゼの基質であるメテニルテトラヒドロメタノプテリンのモデルとしてN,N'-イミダゾリニウムカチオンを用い，金属錯体触媒による水素化反応を検討した。塩基存在下で基質へのヒドリド移行が進行し，生成物とプロトンドナーとを反応させると逆反応により水素が発生した。触媒やイミダゾリニウム誘導体の検討を行い，反応機構について素反応に基づいた考察を行った。

    DOI

  • Extraction ability and mechanism of a sulfur-bridged dithiophenol-based derivative as a Pd(II) extractant

    M. Yamada, K. Onodera, K. Okada, K. Shinoda, H. Seino, A. Shibayama, F. Hamada

    Journal of Molecular Structure ( Elsevier )  1351   2026.02  [Refereed]

    Research paper (journal)   Domestic Co-author

    The recovery of Pt-group metals (PGMs) from spent products is vital owing to their essential roles in electronics, automotive catalysts, and other applications. Extractants with high selectivity, effective extraction ability, and high extraction capacity are required for efficient PGM recovery. Our group previously synthesized and evaluated a dithiophenolic ligand with a S-bridged sulfide moiety (extractant 1) for Pd(II) extraction. We then synthesized an analog of 1, extractant 2, to evaluate its Pd(II) extraction mechanism. Unfortunately, this mechanism could not be clearly elucidated because of inconsistencies between the structure of the extractant–Pd complex inferred by 1H nuclear magnetic resonance (NMR) spectroscopy and that determined by single-crystal X-ray diffraction analysis. Hence, seeking to clarify the mechanism of 2, in this study, we used X-ray absorption spectroscopy in combination with X-ray absorption fine structure (XAFS) analysis to estimate the coordination environment around Pd(II). Firstly, the Pd(II) extraction ability of 2 was evaluated using a single Pd(II) component solution and the leachate of a spent automotive catalyst. Subsequently, the XAFS measurements revealed that the structures of the 2–Pd(II) complex in the solution and crystalline states were identical. Variable-temperature (VT) NMR spectroscopy was applied to determine the exchange rates of the mirror-images of the complex at equilibrium. Pd(II) was extracted via bidentate coordination exchange with Pd–S bond formation and cleavage between the Pd(II) center and two thiomethyl groups in solution at room temperature from the results of the XAFS and VT NMR analyses.

    DOI

  • Structural determination, DFT calculation, and formation mechanism of ethyl 2-cyano-3-alkoxypent-2-enoates synthesized via Ru-mediated coupling reaction between α,β-unsaturated acetals and cyanoacetate

    Hidetake Seino, Takumi Kondo, Chihiro Mochizuki, Ken Tokunaga, Motowo Yamaguchi, Mitsunobu Sato

    Bulletin of the Chemical Society of Japan   90 ( 1 ) 79 - 87   2017.01  [Refereed]

    Research paper (journal)   Domestic Co-author

    [RuHCl(CO)(PPh3)3]を触媒として、α,β-不飽和アセタールとシアノ酢酸エステルから2-シアノ-3-アルコキシペント-2-エン酸エチルを中程度の収率で合成した。E/Z-異性体を分離し、それぞれの構造を単結晶X線回折法で初めて明らかにするとともに、分光学的方法と理論計算から分子構造について考察した。

    DOI

  • N-Heterocyclic carbenes as supporting ligands in transition metal complexes of N2

    Yasuhiro Ohki, Hidetake Seino

    Dalton Transactions   45 ( 3 ) 874 - 880   2015.11  [Refereed]  [Invited]

    Research paper (journal)   Domestic Co-author

    N-ヘテロ環状カルベン（NHCs）は、配位化学や均一系触媒における補助配位子として、適用範囲が近年拡大している。本論文は、NHCで修飾された遷移金属−分子状窒素錯体と、それを利用した触媒的窒素固定反応について、これまでにあった報文をまとめた総説である。

    DOI

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    ◆Introduction and explanation【 display / non-display 】

  • Activation of unsaturated small molecules by bio-relevant multinuclear metal-sulfur clusters

    Kazuki Tanifuji, Shun Ohta, Yasuhiro Ohki, Hidetake Seino

    Coordination Chemistry Reviews ( Elsevier )  475   2023.01  [Refereed]

    Introduction and explanation (scientific journal)   Domestic Co-author

    The high affinity of sulfur (S) for transition metal ions (M), as well as the flexible M－S bonding and bridging modes, enable the formation of a wide range of multi-metallic compounds called metal-sulfur (M－S) clusters. Even though M－S clusters tolerate various nuclearities in principle, the number of metals in molecular entities, particularly those applicable in catalytic reactions, are typically 4 or lower, while the highest number of 8 has been found in the biological N<sub>2</sub>-reducing catalyst. Other than the N<sub>2</sub> reduction, M－S clusters in nature have been found in the conversion of small molecules such as CO<sub>2</sub>, CO, and H<sub>2</sub>. With the detailed structures of these native M－S clusters elucidated by recent biochemical studies, we can take steps toward the development of artificial catalysts superior to enzymes and/or those for biologically inaccessible reactions, while another direction is to deeply understand the enzymatic reactions and their relationship between the M－S structures. Here we review the progress in the reaction studies on synthetic M－S clusters, focusing on their utility in the activation and transformation of small molecules. The main part of this review has been divided into three sections: i) transformations of N<sub>2</sub> and related small molecules, ii) reduction of CO<sub>2</sub>, and iii) transformations of organic small molecules. Remarkable recent progress includes the development of catalytic N<sub>2</sub>-silylation toward N(SiMe<sub>3</sub>)<sub>3</sub> and CO<sub>2</sub> reduction toward C<sub>1</sub>–C<sub>4</sub> hydrocarbons. Tandem reduction and N-methylation of nitroarenes have also been accomplished in the last decade. Through the review process, the development of catalytic reactions by M－S clusters was found to be still challenging. Collaborative works among chemists who can synthesize M－S clusters, those who are skilled in developing homogeneous catalytic reactions, those having spectroscopic techniques, and theoretical chemists may provide new insights into this field.

    DOI

  • Metal-Sulfur Clusters with Relevance to Organometallic Chemistry for Small Molecule Activation and Transformation

    Tanifuji Kazuki, Ohki Yasuhiro, Seino Hidetake

    Journal of Synthetic Organic Chemistry, Japan ( The Society of Synthetic Organic Chemistry, Japan )  80 ( 9 ) 854 - 867   2022.09  [Refereed]

    Introduction and explanation (scientific journal)   Domestic Co-author

    DOI CiNii Research

  • Transition metal-sulfido clusters in nitrogen fixation

    Hidetake Seino

    Sulfuric acid and industry ( The Sulfuric Acid Association of Japan )  71 ( 3 ) 35 - 47   2018.03

    Introduction and explanation (others)   Single author

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Books 【 display / non-display 】

  • Transition Metal-Dinitrogen Complexes; Chapter 2: Group 4 Transition Metal-Dinitrogen Complexes

    Hidetake Seino, Yuji Kajita

    Wiley-VCH  2019.01 ISBN: 978-3-527-34427-7

    ４族遷移金属−窒素錯体の合成，物性，反応について、2018年初めまでの文献を網羅した総説である。

  • Encyclopedia of Coordination Compounds

    Hidetake Seino

    Asakura Publishing Co., Ltd.  2019.09 ISBN: 978-4-254-14105-4

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Grant-in-Aid for Scientific Research 【 display / non-display 】

  • Grant-in-Aid for Scientific Research(C)

    Project Year： 2013.04  -  2016.03  Investigator(s): Hidetake Seino

  • Grant-in-Aid for Scientific Research(C)

    Project Year： 2016.10  -  2019.03  Investigator(s): Hidetake Seino

  • Grant-in-Aid for Scientific Research(C)

    Project Year： 2022.04  -  2025.03  Investigator(s): Hidetake Seino

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Presentations 【 display / non-display 】

  • Synthesis of Pentanuclear Metal–Sulfur Clusters Related to the Structure of C-Cluster in CO Dehydrogenase

    山本采花, 清野秀岳

    第70回 有機金属化学討論会  (大阪公立大学　中百舌鳥キャンパス)  2024.09  -  2024.09  近畿化学協会　有機金属部会

    CO2をCOへ変換することが知られる金属酵素COデヒドロゲナーゼは、活性部位としてCクラスターと呼ばれる、金属原子5つと硫黄原子4つから成る特異なクラスター構造を持つ。金属と硫黄4原子ずつからなる立方体型のクラスター構造は、天然に広く見られ、多くの合成例があるが、Cクラスターのような５核構造の人工的な合成は未だ達成されていない。本研究では、安定なM4S4キュバン型構造に第５の金属を導入 することによって、キュバノイド型５核クラスターの合成を達成した。初めに、キュバン型クラスター[(Cp*Ir)3(CymRu)S4][PF6]2 (Cp* = C5Me5, Cym = p-iPrC6H4Me)のRuサイトに配位子置換によってPh2PCH2PPh2 (dppm)を組み込み、[(Cp*Ir)3{Ru(MeCN)(dppm)}S4][PF6]2を得た。これにPd(dba)2 (dba =(PhCH=CH)2CO)を反応させたところ、dppmがRuとPdを架橋することによって、Pdを取り込んだキュバノイド型５核クラスター[(Cp*Ir)3{Pd(dppm)Ru(MeCN)2}S4][PF6]2が生成した。このクラスターのRu-S結合を１つ取り除くと、クラスター骨格の形態はCクラスターのものとよく一致する。このクラスターは熱力学的に不安定で、室温でゆっくりと[(Cp*Ir)3{Pd(dppm)}RuS4][PF6]2に構造変化した。

  • Selective hydrogenation of nitroarenes catalyzed by ruthenium–sulfur clusters

    村上楠菜, 清野秀岳

    令和６年度化学系学協会東北大会  (秋田大学　手形キャンパス)  2024.09  -  2024.09  日本化学会東北支部

  • Diverse Coordination Modes of Bidentate Phosphine Ligands to the Cubane-Type Ru4S42+ Cluster

    Hidetake Seino, Kenta Toda, Nana Murakami, Naoto Shindo

    The 104th CSJ Annual Meeting  (Funabashi Campus, Nihon University College of Science and Technology)  2024.03  -  2024.03  Chemical Society of Japan

  • Differentiation of the ruthenium sites in cubane-type Ru4S4 clusters

    H. Seino, N. Shindo, S. Kanai, M. Okazaki

    第43回錯体化学国際会議  (仙台)  2018.07  -  2018.08 

    This work demonstrates ligand exchange reactions of a cubane-type Ru4S4 cluster with various tertiary phosphines. These reactions result in differentiation of the coordination environments of Ru sites in a homometallic cluster.

  • Synthesis of the Site-differentiated Tetraruthenium Cubane-type Sulfido Clusters

    Hidetake Seino, Naoto Shindo, Masaaki Okazaki

    The 64th Symposium on Organometallic Chemistry, Japan  2017.09  -  2017.09 

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Academic Activity 【 display / non-display 】

  • 2023.04
    -
    2026.03

  • Chemical Society of Japan

    2023.04
    -
    2026.03

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