Updated on 2026/05/12

写真a

 
HOU ZHAOMIN
 
Organization
School of Materials and Chemical Technology Visiting Professor
Title
Visiting Professor
External link

Degree

  • Doctor of Engineering

Research Interests

  • 錯体触媒

  • 高分子合成

  • 有機合成

  • 有機金属化学

  • Transition metal catalysis

  • Polymerization

  • Organic Synthesis

Research Areas

  • Nanotechnology/Materials / Synthetic organic chemistry

Education

  • Kyushu University   Ph.D.

    1989

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  • China University of Petroleum   B.Sc.

    1982

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  • 中国石油大学   石油精製学部   卒業

    1982

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    Country: China

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  • Kyushu University   M.Sc.

    1986

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  • 九州大学大学院   工学研究科   修士課程修了

    1986

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  • 九州大学大学院   工学研究科   博士課程修了、工学博士取得

    1989

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    Country: Japan

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Research History

  • RIKEN   Center for Sustainable Resource Science   Deputy Center Director

    2013

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  • RIKEN   Center for Sustainable Resource Science Advanced Catalysis Research Group   Group Director

    2013

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  • Tokyo Institute of Technology   Visiting Professor

    2008

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  • Saitama University   Graduate School of Science and Engineering   Visiting Professor

    2003

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  • RIKEN   Cluster for Pioneering Research Organometallic Chemistry Laboratory   Chief Scientist

    2002

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  • RIKEN   Senior Scientist

    1997

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  • RIKEN   Research Scientist

    1993

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  • University of Windsor, Canada   Postdoctoral Researcher

    1991

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  • RIKEN   Special Postdoctoral Researcher

    1990

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  • RIKEN   Postdoctoral Researcher

    1989

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Professional Memberships

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Papers

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Books

  • 刺激応答性高分子の開発動向

    西浦 正芳, 侯 召民(第11章 1 希土類触媒による新しい自己修復ポリマーの開発)

    シーエムシー出版  2021  ( ISBN:9784781316116

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    Total pages:vi, 323p   Responsible for pages:201-208   Language:Japanese  

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  • Comprehensive coordination chemistry III

    Zhenbo Mo, Zhaomin Hou(Lanthanum)

    Elsevier  2021  ( ISBN:9780081026885

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    Total pages:9 v.   Responsible for pages:73-96   Language:English  

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  • 自己修復材料、自己組織化、形状記憶材料の開発と応用事例

    西浦 正芳, 侯 召民(第16節 希土類触媒による新しい自己修復ポリマーの開発)

    技術情報協会  2020  ( ISBN:9784861047817

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    Total pages:446p   Responsible for pages:121-126   Language:Japanese  

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  • ポリマーの強靱化技術最前線 : 破壊機構、分子結合制御、しなやかタフポリマーの開発

    西浦 正芳, 侯 召民(第2編 第1章 第2節 新規希土類触媒を用いたオレフィン系自己修復材料の開発)

    エヌ・ティー・エス  2020  ( ISBN:9784860436681

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    Total pages:xii, ii, vi, 284, ixp   Responsible for pages:133-140   Language:Japanese  

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  • Computational quantum chemistry : insights into polymerization reactions

    Xiaohui Kang, Yi Luo, Zhaomin Hou(Chapter 10 - Theoretical Insights into Olefin Polymerization Catalyzed by Cationic Organo Rare-Earth Metal Complexes)

    Elsevier  2019  ( ISBN:9780128159835

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    Total pages:xv, 368 p.   Responsible for pages:327-356   Language:English  

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  • 構造制御による革新的ソフトマテリアル創成 : ブロック共重合体の精密階層制御・解析・機能化

    西浦 正芳, 侯 召民(3章 希土類錯体触媒を用いたブロック共重合体の合成)

    2018  ( ISBN:9784759813890

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    Total pages:vi, 210p, 図版 [4] p   Responsible for pages:69-75   Language:Japanese  

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  • Nitrogen Fixation (Topics in Organometallic Chemistry, 60)

    Takanori Shima, Zhaomin Hou(Dinitrogen Fixation by Transition Metal Hydride Complexes)

    Springer  2017  ( ISBN:3319577131

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    Total pages:245   Language:English  

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  • Recent development in clusters of rare earths and actinides : chemistry and materials

    Takanori Shima, Zhaomin Hou(Molecular Rare Earth Hydride Clusters)

    Springer  2016  ( ISBN:9783662533017

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    Total pages:ix, 339 p.   Responsible for pages:315-336   Language:English  

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  • 水素利用技術集成 Vol.4, 高効率貯蔵技術、水素社会構築を目指して

    島 隆則, 侯 召民(第2章 第2節 2.3 分子性多金属ヒドリドクラスターの合成と水素吸蔵性能)

    2014  ( ISBN:9784864690829

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    Total pages:19, ii, vii, 332, 10p   Responsible for pages:221-228   Language:Japanese  

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  • New and Future Developments in Catalysis, Activation of Carbon Dioxide

    Liang Zhang, Zhaomin Hou(Chapter9;Transition-Metal-Catalyzed C—C Bon;Forming Reactions with Carbon Dioxide)

    Elsevier  2013 

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    Responsible for pages:253-273  

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  • 希土類の材料技術ハンドブック : 基礎技術・合成・デバイス製作・評価から資源まで

    西浦 正芳, 侯 召民(第3節 1. 希土類触媒による高分子重合)

    エヌ・ティー・エス  2008  ( ISBN:9784860431945

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    Total pages:4, 14, 978, 10, 28p, 図版8p   Responsible for pages:476-475   Language:Japanese  

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  • Comprehensive organometallic chemistry III

    Zhaomin Hou, Takeshi Ohishi(10.11 - C–C Bond Formation through Reaction of CO2 with C≡C and C=C–C=C)

    Elsevier  2006 

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    Total pages:9000   Responsible for pages:537-555   Language:English  

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  • Multimetallic catalysts in organic synthesis

    Zhaomin Hou(CHAPTER 6 Catalytic and Stoichiometric Transformations by Multimetallic Rare Earth Metal Complexes)

    Wiley-VCH  2004  ( ISBN:9783527308286

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    Total pages:310   Responsible for pages:143-162   Language:English  

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  • 第5版 実験化学講座21 有機遷移金属化合物, 超分子錯体

    侯 召民(2 3族有機金属錯体の合成―ランタノイド、アクチノイド―)

    丸善  2004  ( ISBN:4621073206

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    Total pages:xi, 490p   Responsible for pages:13-32   Language:Japanese  

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  • Science of Synthesis, Compounds of group 7-3 (Mn..., Cr..., V..., Ti..., Sc..., La..., Ac...)

    Zhaomin Hou, Yasuo Wakastuki(Product Class 12: Organometallic Complexes of Scandium, Yttrium and the Lanthanides)

    Thieme  2003  ( ISBN:3131121416

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    Total pages:l, 1070 p.   Responsible for pages:849-942   Language:English  

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  • The Progress of Biotechnology, Metal Complexes and Catalysis

    Zhaomin Hou, Masayoshi Nishiura, Yasuo Wakatsuki(Novel Z-selective head-to-head dimerization of terminal alkynes catalyzed by lanthanide half-metallocene complexes)

    Chinese Science Civilization Publishing House  2002 

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    Responsible for pages:52-55  

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  • 均一系遷移金属触媒によるリビング重合

    侯 召民, 若槻 康雄(第3章 3.4 希土類金属錯体によるスチレンの重合及び共重合)

    IPC  1999 

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    Responsible for pages:337-347  

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MISC

  • C–H functionalization with alkenes, allenes, and alkynes by half-sandwich rare-earth catalysts Reviewed

    Xuefeng Cong, Lin Huang, Zhaomin Hou

    Tetrahedron   135   133323   2023

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    Publisher:Elsevier BV  

    DOI: 10.1016/j.tet.2023.133323

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  • Dinitrogen Activation and Addition to Unsaturated C−E (E=C, N, O, S) Bonds Mediated by Transition Metal Complexes Reviewed

    Qingde Zhuo, Xiaoxi Zhou, Takanori Shima, Zhaomin Hou

    Angewandte Chemie International Edition   62 ( 19 )   e202218606   2023

  • Dinitrogen activation and transformation by multimetallic polyhydride complexes Reviewed

    Takanori Shima, Qingde Zhuo, Zhaomin Hou

    Coordination Chemistry Reviews   472   214766   2022

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    Publisher:Elsevier BV  

    DOI: 10.1016/j.ccr.2022.214766

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  • Electron-deficient boron-based catalysts for C–H bond functionalisation

    Yuanhong Ma, Shao-Jie Lou, Zhaomin Hou

    Chemical Society Reviews   50 ( 3 )   1945 - 1967   2021

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    Publisher:Royal Society of Chemistry (RSC)  

    <p>This review article provides a comprehensive overview to recognise the current status of electron-deficient boron-based catalysis in C–H functionalisations.</p>

    DOI: 10.1039/d0cs00380h

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  • Synthesis and Properties of Self-healing Polyolefin

    西浦 正芳, 侯 召民

    JOURNAL OF THE SOCIETY OF RUBBER SCIENCE AND TECHNOLOGY   94 ( 2 )   52 - 57   2021

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  • ミクロ構造制御による自己修復性ポリオレフィンの創製

    PETROTECH   44   353 - 357   2021

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  • Carboxylation Reactions with Carbon Dioxide Using N‐Heterocyclic Carbene‐Copper Catalysts

    Liang Zhang, Zhenghua Li, Masanori Takimoto, Zhaomin Hou

    The Chemical Record   20 ( 6 )   494 - 512   2020

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  • C5Me4SiMe3基を配位子とするチタン及びクロムヒドリドクラスターの合成と窒素分子の活性

    島 隆則, 侯 召民

    Bulletin of Japan Society of Coordination Chemistry   76   56 - 58   2020

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  • さまざまな環境で自己修復する機能性ポリマーの特徴と事例

    西浦 正芳, 侯 召民

    プラスチックス   70 ( 7 )   43 - 47   2019

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  • 匠が拓く高分子合成の新しい技 C‐H結合の活性化を利用した新奇重合反応

    西浦正芳, 侯召民

    高分子   68 ( 2 )   60‐62   2019

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    J-GLOBAL

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  • Activation and Transformation of Dinitrogen and Organonitrogen Compounds by Multimetallic

    島 隆則, 侯 召民

    触媒=Catalysts & catalysis   61 ( 5 )   285 - 290   2019

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  • Metal-catalyzed C H activation for polymer synthesis and functionalization

    Yang Yang, Masayoshi Nishiura, Haobing Wang, Zhaomin Hou

    Coordination Chemistry Reviews   376   506 - 532   2018

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    Language:English   Publisher:Elsevier BV  

    DOI: 10.1016/j.ccr.2018.08.017

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  • Transition metal promoted carboxylation of unsaturated substrates with carbon dioxide

    Liang Zhang, Zhaomin Hou

    Current Opinion in Green and Sustainable Chemistry   3   17 - 21   2017

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    Language:English   Publisher:Elsevier BV  

    DOI: 10.1016/j.cogsc.2016.11.003

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  • Rare Earth-catalyzed Precision Olefin Copolymerization

    西浦 正芳, 侯 召民

    触媒=Catalysts & catalysis   58 ( 1 )   8 - 14   2016

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    Language:Japanese   Publisher:触媒学会  

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  • 希土類錯体を利用した触媒開発の最先端 (特集 希土類・アクチノイドの化学の今と展望)

    西浦 正芳, 侯 召民

    化学と工業 = Chemistry & chemical industry   69 ( 4 )   318 - 320   2016

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  • Dinitrogen Cleavage and Hydrogenation by Multimetallic Titanium Hydride Complexes

    島 隆則, 侯 召民

    ファインケミカル : 調査・資料・報道・抄録   45 ( 3 )   27 - 32   2016

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  • Half-Sandwich Rare-Earth-Catalyzed Olefin Polymerization, Carbometalation, and Hydroarylation

    Masayoshi Nishiura, Fang Guo, Zhaomin Hou

    Accounts of Chemical Research   48 ( 8 )   2209 - 2220   2015

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    Language:English   Publisher:American Chemical Society (ACS)  

    DOI: 10.1021/acs.accounts.5b00219

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  • 希土類触媒による精密共重合の新展開

    西浦 正芳, 侯 召民

    高分子   63   166 - 168   2014

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  • より良いアンモニア合成法の開発に向けて

    じっきょう 理科資料   76   1 - 4   2014

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  • interview この人に聞く 有機金属の可能性に挑戦する 侯召民博士 理化学研究所 主任研究員

    侯 召民, 佐藤 健太郎

    現代化学   ( 510 )   26 - 31   2013

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  • Synthesis, Structure and Reactivity of Scandium Boryl Complex

    王 保力, 西浦 正芳, 侯 召民

    希土類 = Rare earths   ( 62 )   88 - 89   2013

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    Language:English   Publisher:Japanese Society for Engineering Education  

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  • N-Heterocyclic carbene (NHC)-copper-catalysed transformations of carbon dioxide

    Liang Zhang, Zhaomin Hou

    Chemical Science   4 ( 9 )   3395 - 3403   2013

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  • N-Heterocyclic carbene copper-catalyzed carboxylation of C-B and C-H bonds with carbon dioxide

    Liang Zhang, Zhaomin Hou

    Pure and Applied Chemistry   84 ( 8 )   1705 - 1712   2012

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    Publisher:Walter de Gruyter GmbH  

    N-Heterocyclic carbene (NHC) copper complexes serve as an excellent catalytic system for carboxylation of alkyl-, aryl-, and alkenylboron compounds and some aromatic heterocyclic C-H bonds with carbon dioxide (CO2), to afford various functional-group-containing carboxylic acids or their ester derivatives. Some key reaction intermediates have been isolated and structurally characterized, thus providing important insight into the mechanistic details of these catalytic reactions.

    DOI: 10.1351/pac-con-11-10-33

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    Other Link: https://www.degruyter.com/document/doi/10.1351/PAC-CON-11-10-33/xml

  • Rare-Earth Catalyzed C-H Bond Activation and Alkylation of Pyridines

    関 冰涛, 侯 召民

    希土類 = Rare earths   ( 60 )   156 - 157   2012

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  • Rare-earth dialkyl and dihydride complexes bearing monoanionic ancillary ligands

    JianHua Cheng, ZhaoMin Hou

    Science China Chemistry   54 ( 12 )   2032 - 2037   2011

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  • Sc-Catalyzed Regioselective C-H Bond Silylation of Anisoles

    小山田 重蔵, 西浦 正芳, 侯 召民

    希土類 = Rare earths   ( 58 )   90 - 91   2011

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  • Synthesis and structure of molecular chalcogenido clusters containing rare earth metals

    島 隆則, 侯 召民

    希土類 = Rare earths   ( 58 )   88 - 89   2011

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  • Discovery and development of rare-earth-catalyzed coupling reactions

    NISHIURA Masayoshi, HOU Zhaomin

    ( 56 )   132 - 133   2010.5

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  • Scandium-catalyzed copolymerization of non-conjugated dienes with styrene and ethylene

    GUO Fang, NISHIURA Masayoshi, HOU Zhaomin

    ( 56 )   28 - 29   2010.5

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  • Half-Sandwich Rare Earth Metal Complexes as Novel Catalysts for Olefin Polymerization and Other Chemical Transformations

    Masayoshi Nishiura, Zhaomin Hou

    Bulletin of the Chemical Society of Japan   83 ( 6 )   595 - 608   2010

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    Publisher:The Chemical Society of Japan  

    DOI: 10.1246/bcsj.20100003

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  • Novel polymerization catalysts and hydride clusters from rare-earth metal dialkyls

    Masayoshi Nishiura, Zhaomin Hou

    Nature Chemistry   2 ( 4 )   257 - 268   2010

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    Publisher:Springer Science and Business Media LLC  

    DOI: 10.1038/nchem.595

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    Other Link: http://www.nature.com/articles/nchem.595

  • Organo Rare Earth Complexes in Olefin Polymerization and Organic Synthesis

    HOU Zhaomin

    ( 54 )   134 - 135   2009.5

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  • Recent Progress in Half-sandwich Rare-earth-catalyzed Organic Synthesis

    Toshiaki Suzuki, Wen-Xiong Zhang, Masayoshi Nishiura, Zhaomin Hou

    Journal of Synthetic Organic Chemistry, Japan   67 ( 5 )   451 - 464   2009

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    Language:Japanese   Publishing type:Book review, literature introduction, etc.  

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  • Syntheses and Structures of Rare Earth Metal Polyhydrido Clusters Supported by Cyclopentadienyl Ligands

    島 隆則, 侯 召民

    希土類 = Rare earths   ( 54 )   196 - 197   2009

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  • Reactions of Polynuclear Rare-Earth Metal Polyhydrido Complexes with Cyclooctatetraene

    今野 陽介, 西浦 正芳, 侯 召民

    希土類 = Rare earths   ( 54 )   194 - 195   2009

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  • Alternative and Random Copolymerization of Isoprene with Ethylene by Rare-Earth Metal Catalysts

    西浦 正芳, 李 暁芳, 森 響一, 侯 召民

    希土類 = Rare earths   ( 54 )   192 - 193   2009

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  • Synthesis and Reactivity of Dialkyl Rare Earth Metal Complexes Bearing Mono(pyrrolyl) Ligands

    西浦 正芳, 増子 智洋, 侯 召民

    希土類 = Rare earths   ( 52 )   84 - 85   2008

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  • Hydrogen Uptake at a Single Crystal of Rare-Earth/Transition-Metal Heterometallic Polyhydride Clusters

    島 隆則, 侯 召民

    希土類 = Rare earths   ( 52 )   78 - 79   2008

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  • Multimetallic catalyst based on the rove earth hydride clusters

    島 隆則, 侯 召民

    Japanese scientific monthly   61 ( 1 )   24 - 29   2008

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    Language:Japanese   Publisher:日本学術振興会  

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  • Scandium and yttrium complexes for well-controlled polymerization

    侯 召民, 鈴木 俊彰

    Materials integration   21 ( 1 )   34 - 42   2008

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    Language:Japanese   Publisher:ティー・アイ・シィー  

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  • Catalytic addition of alkyne C–H, amine N–H, and phosphine P–H bonds to carbodiimides: an efficient route to propiolamidines, guanidines, and phosphaguanidines

    Wen-Xiong Zhang, Zhaomin Hou

    Organic & Biomolecular Chemistry   6 ( 10 )   1720 - 1720   2008

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    Publisher:Royal Society of Chemistry (RSC)  

    DOI: 10.1039/b800135a

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  • Organometallic catalysts for copolymerization of cyclic olefins

    Xiaofang Li, Zhaomin Hou

    COORDINATION CHEMISTRY REVIEWS   252 ( 15-17 )   1842 - 1869   2008

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    Language:English   Publishing type:Book review, literature introduction, etc.  

    DOI: 10.1016/j.ccr.2007.11.027

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  • Synthesis of Novel Elastomers by Well-Defined Rare Earth Metal Catalysts

    鈴木 俊彰, 侯 召民

    NIPPON GOMU KYOKAISHI   81 ( 10 )   414 - 418   2008

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    Language:Japanese   Publisher:THE SOCIRETY OF RUBBER SCIENCE AND TECHNOLOGYY, JAPAN  

    The cationic rare earth metal alkyl species bearing a bis (phosphine) amide ancillary ligand, generated by treatment of the corresponding dialkyl complexes with one equivalent of a borate compound can serve as an excellent catalyst for the living &lt;i&gt;cis&lt;/i&gt;-1, 4 polymerization of both isoprene and butadiene as well as for the living &lt;i&gt;cis&lt;/i&gt;-1, 4 copolymerization of isoprene and butadiene. On the other hand, the polymerization of isoprene by the binuclear monocationic monoalkyl species with cyclopentadienyl-phosphide ligands has afforded exclusively isotactic 3, 4-polyisoprene with extremely high regio- and stereoselectivity (3, 4-selectivity: 100%, &lt;i&gt;mmmm&lt;/i&gt;&gt;99%). An amidinate-ligated aminobenzylyttrium complex, in combination with [Ph&lt;sub&gt;3&lt;/sub&gt;C] [B(C&lt;sub&gt;6&lt;/sub&gt;F&lt;sub&gt;5&lt;/sub&gt;)&lt;sub&gt;4&lt;/sub&gt;], is an excellent catalyst system for the isospecific 3, 4-polymerization of isoprene, while the regio- and stereoselectivity of this polymerization system can be dramatically switched from 3, 4-isospecific to 1, 4-&lt;i&gt;cis&lt;/i&gt; selective by the addition of AlMe&lt;sub&gt;3&lt;/sub&gt;. Cationic rare-earth hydride clusters, which are made by treating the corresponding neutral complexes with a borate activator, show high regio- and stereoselectivity for the polymerization of 1, 3-cyclohexadiene (CHD) to afford soluble crystalline &lt;i&gt;cis&lt;/i&gt;-1, 4-linked poly (CHD) unavailable previously. The syndiospecific living copolymerization of styrene with isoprene has been achieved by use of a cationic half-sandwich scandium alkyl catalyst.

    DOI: 10.2324/gomu.81.414

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  • Synthesis and Reactions of Polynuclear Polyhydrido Rare Earth Metal Complexes Containing “(C 5 Me 4 SiMe 3 )LnH 2 ” Units: A New Frontier in Rare Earth Metal Hydride Chemistry

    Zhaomin Hou, Masayoshi Nishiura, Takanori Shima

    European Journal of Inorganic Chemistry   2007 ( 18 )   2535 - 2545   2007

  • Development of Novel Olefin Polymerization Catalysts Based on Well-Defined Organo-Rare-Earth-Metal Complexes

    鈴木 俊彰, 侯 召民

    High Polymers, Japan   56 ( 11 )   915 - 920   2007

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    Language:Japanese   Publisher:The Society of Polymer Science, Japan  

    DOI: 10.1295/kobunshi.56.915

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  • Recent development of the chemistry of organo rare earth metal complexes

    今野 陽介, 侯 召民

    化学工業   58 ( 10 )   799 - 804   2007

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    Language:Japanese   Publisher:化学工業社  

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  • Development of novel polymerization catalysts based on organo rare earth metal complexes

    瀧本 真徳, 侯 召民

    Fine chemicals   36 ( 6 )   17 - 23   2007

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    Language:Japanese   Publisher:シーエムシー出版  

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  • A General Method for the Synthesis of Half-sandwich Bis(alkyl) and Polyhydrido Complexes of the Whole Series of Rare Earth Metals

    西浦 正芳, 侯 召民

    希土類 = Rare earths   ( 50 )   212 - 213   2007

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  • 希土類錯体触媒を利用した新しいポリマー材料の合成

    侯 召民, 瀧本 真徳

    未来材料   7 ( 5 )   24 - 31   2007

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  • New Organo Rare Earth Metal Catalysts for Novel Chemical Transformations

    侯 召民

    化学と工業 = Chemistry and chemical industry   60 ( 3 )   188 - 188   2007

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  • Cationic rare earth metal alkyls as novel catalysts for olefin polymerization and copolymerization

    Zhaomin Hou, Yunjie Luo, Xiaofang Li

    Journal of Organometallic Chemistry   691 ( 14 )   3114 - 3121   2006

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    DOI: 10.1016/j.jorganchem.2006.01.055

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  • Development of Novel Olefin Polymerization Catalysts Based on Organo Rare Earth Metal Complexes

    瀧本 真徳, 侯 召民

    希土類 = Rare earths   ( 49 )   47 - 57   2006

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  • 異国で活躍する研究者(4)私の"異国"滞在記--文化大革命直後の中国から日本へ

    侯 召民

    現代化学   ( 421 )   46 - 50   2006

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  • Theoretical Investigation on the Syndiospecific Polymerization of Styrene by Group 3 (Sc and Y) Half-metallocene Catalysts

    羅 一, 古山 通久, 久保 百司, 宮本 明, 侯 召民

    触媒 = Catalysts & Catalysis   48 ( 2 )   150 - 150   2006

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  • INOR 1030-Location of a 4-coordinate H atom via neutron diffraction

    Robert Bau, Muhammed Yousufuddin, Zhaomin Hou, Olivier Tardif, Jens Baldamus, Sax A. Mason, Garry J. McIntyre, Matthias J. Gutmann

    Abstracts of Papers of the American Chemical Society   232   2006

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  • Hydrogen at the flick of a switch

    Masanori Takimoto, Zhaomin Hou

    Nature   443 ( 7110 )   400 - 401   2006

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    DOI: 10.1038/443400a

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  • Synthesis of non-metallocene dialkyl rare-earth metal complexes and their activity for olefin polymerization

    鈴木 俊彰, 張 立新, 齋藤 真弓, 干鯛 眞信, 侯 召民

    希土類 = Rare earths   46   228 - 229   2005

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  • Alternating Copolymerization of Cyclohexene Oxide and CO_2 by Organo Rare Earth Catalysts

    崔 冬梅, 西浦 正芳, 侯 召民

    希土類 = Rare earths   44   224 - 225   2004

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  • Synthesis, Structure and Unique Reactivity of a Novel Tetrahydrido Tetranuclear Yttrium Complex [(C_5Me_4SiMe_3)Y]_4(μ-H)_4(Me_3SiCCHCHCSiMe_3)

    Tradif Olivier, 侯 召民

    希土類 = Rare earths   44   222 - 223   2004

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  • Organolanthanide catalyzed regio- and stereoselective dimerization of terminal alkynes and polymerization of aromatic diynes

    Masayoshi Nishiura, Zhaomin Hou

    Journal of Molecular Catalysis A: Chemical   213 ( 1 )   101 - 106   2004

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    DOI: 10.1016/j.molcata.2003.10.053

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  • Recent Progress in the Chemistry of Rare Earth Metal Alkyl and Hydrido Complexes Bearing Mono(cyclopentadienyl) Ligands

    Zhaomin Hou

    Bulletin of the Chemical Society of Japan   76 ( 12 )   2253 - 2266   2003

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    Publisher:The Chemical Society of Japan  

    DOI: 10.1246/bcsj.76.2253

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  • New reactions of 1-alkynes catalyzed by transition metal complexes

    Yasuo Wakatsuki, Zhaomin Hou, Tokunaga Makoto

    The Chemical Record3(3)   3 ( 3 )   144 - 157   2003

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    DOI: 10.1002/tcr.10061

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  • Regio-and Stereoselective Polymerization of Aromatic Diynes by Organolanthanide Catalysts

    西浦 正芳, 谷川 真, 星野 幹雄, 宮本 健, 侯 召民

    希土類 = Rare earths   42   54 - 55   2003

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  • Synthesis, Structure and Reactivity of the Polyhydrido Yttrium Cluster Complex [(C_5Me_4SiMe_3)Y(μ-H)_2]_4(THF)

    Tradif Olivier, 倉角 純子, 西浦 正芳, 堀内 昭, 侯 召民

    希土類 = Rare earths   42   50 - 51   2003

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  • Recent developments in organolanthanide polymerization catalysts

    Zhaomin Hou, Yasuo Wakatsuki

    Coordination Chemistry Reviews   231 ( 1-2 )   1 - 22   2002

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    DOI: 10.1016/s0010-8545(02)00111-x

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  • Synthesis, Structures and Catalytic Reactivity of Rare Earth Alkyl and Hydride Complexes Bearing Silylene Bridged Cyclopentadienyl-Phosphido Ligands

    Tradif Olivier, 西浦 正芳, 召民, 若槻 康雄

    希土類 = Rare earths   40   22 - 23   2002

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  • Synthesis and Novel Catalytic Reactivities of Rare Earth Alkyl and Acetylide Complexes Bearing Silylene Bridged Cyclopentadienyl-Phosphido Ligands

    西浦 正芳, 八巻 多恵子, 宮本 健, 侯 召民, 若槻 康雄

    希土類 = Rare earths   40   20 - 21   2002

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  • Lanthanide(II) complexes bearing mixed linked and unlinked cyclopentadienyl–monodentate-anionic ligands

    Zhaomin Hou, Yasuo Wakatsuki

    Journal of Organometallic Chemistry   647 ( 1-2 )   61 - 70   2002

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    Language:English   Publisher:Elsevier BV  

    DOI: 10.1016/s0022-328x(01)01237-2

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  • Synthesis and Novel Polymerization and Copolymerization Reactions of New Organolanthanide Complexes. Reviewed

    Zhaomin Hou

    Journal of Synthetic Organic Chemistry, Japan   59 ( 2 )   82 - 91   2001

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    Publisher:The Society of Synthetic Organic Chemistry, Japan  

    DOI: 10.5059/yukigoseikyokaishi.59.82

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    Other Link: http://orcid.org/0000-0003-2841-5120

  • Catalytic C-C Bond Cleavage of Aromatic Pinacols and Catalytic Michael Additions by a Binuclear Iridium(II) Hydride Complex.

    小泉武昭, 若槻康雄, HOU Z

    日本化学会講演予稿集   79th ( 1 )   2001

  • Novel polymerization and copolymerization of ethylene, styrene, and/or butadiene by new organolanthanide-based catalysts

    Zhaomin Hou, Shojiro Kaita, Yasuo Wakatsuki

    Pure and Applied Chemistry   73 ( 2 )   291 - 294   2001

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    Language:English   Publisher:Walter de Gruyter GmbH  

    Abstract

    Replacement of one of the two C5Me5 ligands in the samarocene (II) complex (C5Me5) 2Sm (THF) 2 with a monodentate anionic ligand (e. g. , OAr, SAr, or NR1R2) gives a unique catalytic system, which can not only polymerize styrene and ethylene, but also copolymerize them into block styrene-ethylene copolymers under the presence of both monomers. On the other hand, addition of an appropriate cocatalyst such as MMAO or AlR3/[Ph3C][B (C6F 5) 4] to the samarocene complex (C5Me5) 2Sm (THF) 2 or (C5Me5) 2Sm (m-Me) 2AlMe2 affords a novel catalytic system for stereospecific 1,4-cis living polymerization of butadiene and copolymerization of butadiene with styrene.

    DOI: 10.1351/pac200173020291

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    Other Link: https://www.degruyter.com/document/doi/10.1351/pac200173020291/xml

  • Synthesis and Some Novel Reactions of Organolanthanide Alkyl, Silyl, and Hydride Complexes

    侯 召民, 張 玉根, Tardif Olivier, 若槻 康雄

    希土類 = Rare earths   ( 38 )   54 - 55   2001

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  • 十字路

    侯 召民, 太田 光昭

    有機合成化学協会誌   59 ( 2 )   150 - 150   2001

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    DOI: 10.5059/yukigoseikyokaishi.59.150

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  • サマロセン触媒系によるブタジエンの立体特異的リビング重合

    会田 昭二郎, 侯 召民, 岩槻 康雄

    触媒=Catalysts & catalysis   43 ( 6 )   443 - 445   2001

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  • C5Me5/ER-Ligated samarium(II) complexes (ER=OAr, SAr, NR1R2): a new type of olefin polymerization catalysts

    Zhaomin Hou, Yasuo Wakatsuki

    Journal of Alloys and Compounds   303-304   75 - 82   2000

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    DOI: 10.1016/s0925-8388(00)00654-x

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  • Synthesis and Catalytic Behavior of Novel Divalent Lanthanide Complexes Bearing Silylene Bridged Bis- and Monocyclopentadienyl Ligands

    小泉 武昭, 謝 鵬, Tardif Olivier, 侯 召民, 若槻 康雄

    希土類 = Rare earths   ( 36 )   172 - 173   2000

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  • Novel Reactions of Divalent Lanthanide Complexes with Arylimines

    小泉 武昭, 依田 智香子, 侯 召民, 福沢 信一, 若槻 康雄

    希土類 = Rare earths   ( 34 )   284 - 285   1999

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  • Reactions of Ketones with Low-Valent Lanthanides: Isolation and Reactivity of Lanthanide Ketyl and Ketone Dianion Complexes

    Zhaomin Hou, Yasuo Wakatsuki

    Topics in Organometallic Chemistry (Springer-Verlag)   2   234   1999

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  • Ring-Opening Polymerization and Copolymerization of Lactones by Samarium(II) Aryloxide Complexes

    西浦 正芳, 侯 召民, 今本 恒雄, 若槻 康雄

    希土類 = Rare earths   ( 34 )   198 - 199   1999

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  • シクロペンタジエニルなどを配位子とする2価ランタノイド錯体の合成と反応 (ランタノイドを利用する有機合成) -- (2価のランタノイド反応剤を用いる合成)

    侯 召民, 若槻 康雄

    季刊化学総説   37 ( 37 )   53 - 62   1998

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  • Trapping of Radicals in the Coordination Spheres of Metals

    Zhaomin Hou, Yasuo Wakatsuki

    Chemistry - A European Journal   3 ( 7 )   1005 - 1008   1997

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    Language:English   Publisher:Wiley  

    DOI: 10.1002/chem.19970030704

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  • Low-Valent Rare Earth Elements in Synthetic Organic Reactions

    侯 召民

    希土類 = Rare earths   ( 30 )   224 - 225   1997

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  • Lanthanide(II) Aryloxide-Catalyzed Hydroboration of Alkenes and Polymerizations of Styrene and Ethylene

    侯 召民, 張 玉根, 若槻 康雄

    希土類 = Rare earths   ( 30 )   40 - 41   1997

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  • Synthesis, Structural Characterization and Reactivity of Aryloxide-Based Heteroleptic Samarium(II) Complexes

    侯 召民, 吉村 啓, 若槻 康雄

    希土類 = Rare earths   ( 28 )   290 - 291   1996

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  • One-Electron Reduction of Diaryl Ketones by Lanthanide(II) Amide Complexes

    藤田 晶, 侯 召民, 山崎 博史, 若槻 康雄

    希土類 = Rare earths   ( 28 )   292 - 293   1996

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  • Synthesis, Structural Characterization and Reactivity of Lanthanide-Ketyl Complexes

    侯 召民, 宮野 隆徳, 山崎 博史, 若槻 康雄

    希土類 = Rare earths   ( 26 )   314 - 315   1995

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  • Low Valent Lanthanides in Organic Synthesis. Ligand Effects on the Reactivity of Some Divalent and Trivalent Samarium and Ytterbium Complexes. Reviewed

    Zhaomin Hou, Yasuo Wakatsuki

    Journal of Synthetic Organic Chemistry, Japan   53 ( 10 )   906 - 916   1995

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Industrial property rights

  • New polymers and production of same.

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    Application no:特願2015-040111 

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  • Physical and mechanical properties of polar olefin polymer and copolymer

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    Application no:特願2018-046829 

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  • Production method for polar olefin polymer and copolymer

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    Application no:PCT/JP2018/010009 

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  • Ammonia synthesis catalyst, and use thereof

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    Application no:JP2018/008764 

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Awards

  • Japan Academy Prize

    2022  

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  • Chemical Society of Japan Awards

    2019  

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  • Asian Core Program/Advanced Research Network (Hong Kong)

    2018  

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  • Swiss Chemical Society (SCS) Lectureships

    2018  

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  • Nagoya Silver Medal

    2016  

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  • Chinese Chemical Society Yaozeng Huang Award in Organometallic Chemistry

    2014  

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  • Seventh Negishi-Brown Lectures, Purdue University

    2014  

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  • Pioneers from Asia, The 15th Asian Chemical Congress

    2013  

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  • The Award of the Society of Polymer Science, Japan

    2012  

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  • Asian Core Program Lectureship Award (Singapore)

    2012  

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  • Asian Core Program Lectureship Award (China)

    2011  

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  • Asian Core Program Lectureship Award (Taiwan)

    2011  

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  • The Rare Earth Society of Japan Award

    2009  

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  • The Commendation for Science and Technology by the Minister of Education, Culture, Sports, Science and Technology: the Prizes for Science and Technology in Research Category

    2008  

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  • JSPS Prize

    2007  

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  • Mitsui Chemicals Catalysis Science Award

    2007  

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  • The Chemical Society of Japan Award for Creative Work

    2007  

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  • Progress Award in Synthetic Organic Chemistry, Japan

    2000  

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    Country:Japan

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  • Rare Earth Society of Japan Award for Young Scientists

    1997  

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    Country:Japan

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  • Japan Society of Coordination Chemistry Award for Young Scientists

    1996  

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Research Projects

  • 希土類触媒による革新的自己修復ポリマーの創製

    Grant number:23H00300  2023.4 - 2027.3

    日本学術振興会  科学研究費助成事業  基盤研究(A)

    侯 召民

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    Grant amount:\46670000 ( Direct Cost: \35900000 、 Indirect Cost:\10770000 )

    本研究では、研究代表者らがこれまでの研究で得た独自の知見を基に、希土類触媒の特長を生かした革新的な自己修復材料の創出を目指す。具体的には、様々な有機希土類錯体触媒を活用し、極性オレフィンと非極性オレフィンとの共重合や、性質の異なる様々なオレフィン類やジエン類などの共重合を精密に制御し、ミクロ相分離の誘起による優れた自己修復機能の発現に加え、耐熱性や耐寒性、接着性、発光性、導電性など様々な機能を付与した付加価値の高い新機能ポリマー群を創製する。
    本年度は、ハーフサンドイッチ型スカンジウム触媒を用いて、発光ユニットとしてスチリルピレン基を組み込んだモノマーとアニシルプロピレンとエチレンとの三元共重合を行うことにより、高い蛍光量子収率で発光し、ゴムのように伸縮する自己修復性材料の開発に成功した。自己修復性を引張試験で評価したところ、24時間で引っ張り強度が完全に回復し、アニシルプロピレンとエチレンの二元共重合体の自己修復時間(5日間)と比べて、自己修復速度が向上した。また、この材料に特定の波長の光を照射すると、スチリルピレン基内の炭素―炭素二重結合の[2+2]環化付加が進行して蛍光特性を制御することができる。この特徴を生かしたフォトリソグラフィーによって、フィルム状にした材料の表面に二次元画像を転写させることに成功した。自然光では転写した形を認識することはできないが、紫外線を照射することによって形を認識できることから、情報記憶デバイスとしての応用が考えられる。

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  • Development of Enantioselective Carboalumination of Alkenes and Alkynes Catalyzed by Rare-Erath Metal Catalysts

    Grant number:21F21334  2021.11 - 2024.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for JSPS Fellows

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    Grant amount:\2200000 ( Direct Cost: \2200000 )

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  • Synthesis of Mid- and Late-Transition Metal Hydride Complexes for N2 Activation and Functionalization

    Grant number:21F20037  2021.4 - 2023.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for JSPS Fellows

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    Grant amount:\2300000 ( Direct Cost: \2300000 )

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  • 中-後周期遷移金属ヒドリド錯体の合成と窒素分子の活性化および官能基化

    Grant number:20F40037  2020.11 - 2022.3

    日本学術振興会  科学研究費助成事業  特別研究員奨励費

    侯 召民, ZHOU XIAOXI

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    Grant amount:\2300000 ( Direct Cost: \2300000 )

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  • 中-後周期遷移金属ヒドリド錯体の合成と窒素分子の活性化および官能基化

    Grant number:20F20037  2020.4 - 2022.3

    日本学術振興会  科学研究費助成事業  特別研究員奨励費

    侯 召民, ZHOU XIAOXI

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    Grant amount:\2300000 ( Direct Cost: \2300000 )

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  • Development of New Chemical Transformations by Rare Earth Catalysts

    Grant number:19H00897  2019.4 - 2022.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (A)

    Hou Zhaomin

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    Grant amount:\45370000 ( Direct Cost: \34900000 、 Indirect Cost:\10470000 )

    This project aimed to develop new catalysts, new reactions and new functional materials superior or complementary to the existing ones. By using half-sandwich rare-earth catalysts, we have achieved for the first time the terpolymerization of ethylene and two different methoxyaryl-substituted propylenes in a controlled fashion, which afforded new functional polyolefins with excellent self-healing property. We have synthesized a series of chiral half-sandwich rare-earth alkyl complexes that show excellent enantioselectivity and activity in various transformations such as asymmetric dearomative annulation of quinolines with alkynes and asymmetric exo-selective annulation of imidazoles with 1,1-disubstituted alkenes via C-H activation.

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  • 新規チタン錯体の合成と窒素分子活性化への展開

    Grant number:18F18333  2018.11 - 2021.3

    日本学術振興会  科学研究費助成事業  特別研究員奨励費

    侯 召民, MO ZHENBO

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    Grant amount:\2400000 ( Direct Cost: \2400000 )

    Studies on N2 activation by transition metal hydride complexes are of particular interest and importance, but studies on well-defined N2 metal hydride complexes are still very limited. We report the synthesis and diverse transformations of a N2 dititanium hydride complex bearing the rigid acridane-based acriPNP-pincer ligands. This complex enabled N2 cleavage and hydrogenation even without additional reagents. Furthermore, diverse transformations of the N2 unit with a variety of organometallic compounds have been well established at the rigid acriPNP-ligated dititanium framework. This work has revealed many unprecedented aspects of N2 reaction chemistry, and may help open a new avenue for the design and synthesis of well-defined metal hydride complexes for N2 fixation and transformation.

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  • Development of Domino Catalyst merged with organic synthesis and polymerization

    Grant number:17H06451  2017.6 - 2022.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)

    Hou Zhaomin

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    Grant amount:\79560000 ( Direct Cost: \61200000 、 Indirect Cost:\18360000 )

    This project aimed to develop new catalysts, new reactions and new functional materials superior or complementary to those existing. By using half-sandwich rare-earth catalysts, we have achieved for the first time the terpolymerization of ethylene and two different methoxyaryl-substituted propylenes in a controlled domino reaction fashion, which afforded a new family of functional polyolefins with excellent self-healing property. We have synthesized a series of chiral half-sandwich rare-earth alkyl complexes that show excellent enantioselectivity and activity in various transformations such as asymmetric dearomative annulation of quinolines with alkynes and asymmetric exo-selective annulation of imidazoles with 1,1-disubstituted alkenes via C-H activation. We have achieved efficient and selective difunctionalization of imines via CO2 activation by an N/B Lewis pair under copper catalysis.

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  • Development of New Catalysts Based on Half-Sandwich Metal Complex Structures

    Grant number:26220802  2014.5 - 2019.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (S)

    Hou Zhaomin

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    Grant amount:\194870000 ( Direct Cost: \149900000 、 Indirect Cost:\44970000 )

    This project aimed to develop new catalysts, new reactions and new functional materials superior or complementary to the existing ones. By using half-sandwich rare-earth catalysts, we have achieved for the first time the copolymerization of ethylene and polar alpha-olefins in a controlled fashion, which afforded new functional polyolefins with excellent self-healing and shape-memory properties. We have synthesized a series of chiral half-sandwich rare-earth alkyl complexes that show excellent enantioselectivity and activity in various transformations such as asymmetric C-H, N-H and Si-H alkylation via C=C insertion. By using molecular metal hydride clusters, we have achieved the activation and transformation of inactive small molecules and aromatic skeletons under mild conditions such as conversion of N2 to nitriles and hydrodenitrogenation of pyridine. This work has not only opened up new avenues in chemical science, but may also offer new entries into chemical industry innovation.

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  • 多金属ヒドリド錯体を基盤とする新反応場の構築

    Grant number:26248021  2014.4 - 2017.3

    日本学術振興会  科学研究費助成事業  基盤研究(A)

    侯 召民

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    Grant amount:\21190000 ( Direct Cost: \16300000 、 Indirect Cost:\4890000 )

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  • Development of Novel Catalysts Based on Organo Rare Earth Metal Complexes

    Grant number:21225004  2009.5 - 2014.3

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (S)

    HOU Zhaomin

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    Grant amount:\212680000 ( Direct Cost: \163600000 、 Indirect Cost:\49080000 )

    By use of the cationic half-sandwich rare earth alkyl catalysts, we have achieved the regio- and stereoselective copolymerization of various olefins to give new polymer materials that cannot be prepared by previous means. The cationic half-sandwich rare-earth alkyl complexes can also serve as unique catalysts for the addition of ortho-C-H bonds of various pyridines and anisoles to a variety of olefins, to afford new alkylated pyridine and anisole derivatives, respectively.
    We have synthesized a new family of heteromultimetallic polyhydride complexes and group 4 metal polyhydride complexes, and found that rare-earth/d-transition metal heteromultimetallic polyhydride complexes and a trinuclear titanium hydride cluster show reversible hydrogen addition and release reaction, and unprecedented dinitrogen activation, respectively.

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  • 希土類元素をベースとする多金属触媒の開発

    Grant number:21245017  2009

    日本学術振興会  科学研究費助成事業  基盤研究(A)

    侯 召民

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    Grant amount:\22880000 ( Direct Cost: \17600000 、 Indirect Cost:\5280000 )

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  • Multimetallic Catalysts Based on Rare Earth Hydride Clusters

    Grant number:18065020  2006 - 2009

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research on Priority Areas

    HOU Zhaomin

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    Grant amount:\32000000 ( Direct Cost: \32000000 )

    The discovery of new catalysts can result in breakthroughs in various areas. Based on the multimetallic rare earth metal complexes, we have achieved for the first time the selective formation of ethylene from carbon monoxide, the regio^- and stereoselective cross-coupling reaction of terminal alkynes with isocyanides, and regio^- and stereoselectivity switching in isoprene polymerization. We have also found that the Y_4-Mo pentanuclear polyhydride complex can reversibly uptake and release hydrogen in an unprecedented fashion.

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  • Development of novel catalysts based on rare earth complexes

    Grant number:18205010  2006 - 2008

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (A)

    HOU Zhaomin

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    Grant amount:\50700000 ( Direct Cost: \39000000 、 Indirect Cost:\11700000 )

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  • New Polymerization Reactions by Dynamic Rare Earth Complexes

    Grant number:14078224  2002 - 2005

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research on Priority Areas

    HOU Zhaomin

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    Grant amount:\24800000 ( Direct Cost: \24800000 )

    1. Synthesis of Rare Earth Metal Bis(alkyl) Complexes and Conversion into Cationic Mono(alkyl) Active Species : Recently, considerable attention has been directed to rare earth metal bis(alkyl) complexes, since such complexes or cationic mono(alkyl) species prepared from them are expected to provide a sterically and electronically more unsaturated metal center and thus to show unique reactivity that differs from those of the conventional metallocenens. In this study, a series of half-sandwich rare earth metal bis(alkyl) complexes have been successfully prepared from Ln(CH_2SiMe_3)_3 (2thf) and C_5Me_4HSiMe_3. Binuclear rare earth metal bis(alkyl) complexes, in which the two metal centers are bridged by two phosphido ligands, and non-metallocene yttrium bis(alkyl) complexes have also been obtained in an analogous way. These bis(alkyl) complexes can be readily converted to the corresponding cationic mono(alkyl) species by treating with 1 equiv of [Ph_3C][B(C_6F_5)_4].
    2. Development of Highly Selective Copolymerization Reactions Catalyzed by Cationic Rare Erath Metal Mono(alkyl) Species : These cationic rare earth metal species can act as excellent catalysts for the region-and stereospecific polymerization and copolymerization of various olefins. They exhibit excellent activities and selectivity for syndiospecific copolymerization of styrene with ethylene, alternating copolymerization of ethylene with norbornene or dicyclopentadiene, and isospecific 3,4-polymerization and living cis-1,4-polymerization of isoprene. Most of these polymerization reactions are unique to the rare earth metal catalysts, and are difficult to achieve by previously known catalyst systems.
    3. Synthesis of Rare Earth Metal Hydride Clusters and Studies on Synergistic Reactivity of These Complexes : In the course of these studies, we found that the half-sandwich rare earth metal bis(alkyl) complexes can readily react with H_2 to afford the corresponding tetranuclear octahydrido complexes. These hydride clusters exhibit high reactivities towards various multiple bonds. For example, the reaction with carbon monoxide afforded selectively ethylene under mild conditions.

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  • Development of new rare earth metal polymerization catalysts

    Grant number:13440203  2001 - 2004

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (B)

    HOU Zhaomin, KAITA Shojiro, NISHIURA Masayoshi

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    Grant amount:\5600000 ( Direct Cost: \5600000 )

    1.1,4-Cis stereospecific polymerization of 1,3-butadiene by samarocene catalysts
    The C_5Me_5R-ligated samarocene(II) complexes, (C_5Me_4R)_2Sm(THF)_x(1, R=Me ; 2, R=Et ; 3, R=i-Pr, 4, R=n-Bu, 5 ; R=TMS ; x=1 or 2), in combination with modified methylaluminoxane(MMAO) were examined in cyclohexane with respect to their catalytic performances for the polymerization of butadiene. Complexes 2-5 showed considerable promotion in both catalytic activity and regularity of the resulting polymer as compared to parent 1 : activity,3>>5〜4>2>1 ; 1,4-cis selectivity at 50℃,3〜5>4>2>1.
    2.1,4-Cis stereospecific polymerization of 1,3-butadiene by cationic rare earth metallocene catalysts
    Cationic metallocene complexes[(C_5Me_5)_2Ln][B(C_6F_5)_4](Ln=Pr, Nd, Gd) in combination with ^iBu_3Al efficiently induce highly 1,4-cis specific polymerization of butadiene. The activity of the Gd complex/^iBu_3Al system is high enough to exhibit good catalytic activity even at low temperature. Polymerization at -78℃ gave polybutadiene with nearly perfect 1,4-cis microstructure (>99.9%) with sharp molecular weight distribution (M_w/M_n=1.45) and in reasonable yield.
    3.Synthesis, Structural Characterization, and Novel Catalysis of Rare Earth Alkyl Complexes Bearing Silylene-Linked Cyclopentadienyl-Phosphido Ligands
    The reactions of Ln(CH_2SiMe_3)_3(THF_2)(Ln=Y, Yb, Lu) with 1 equiv of Me_2Si(C_5Me_4H)(PHR)(R=Ph, Cy) afforded the first silylene-linked cyclopentadienylphosphido rare earth alkyl complexes, [Me_2Si(C_5Me_4)(μ-PR)Ln(CH_2SiMe_3)]_2. In contrast with the analogous cyclopentadienyl-amido and metallocene complexes, these complexes adopt a dimeric structure through phosphide bridging, while the alkyl ligand is placed in a terminal position. Owing to their unique steric and electronic ligand environments, most of these complexes showed much higher activity for the polymerization of ethylene and hydrosilylation of olefins than that of the conventional metallocene or amido analogues. Moreover, when treated with [Ph_3C][B(C_6F_5)_4], these complexes showed extremely high regio- and stereoselectivity for the 3,4-polymerization of isoprene, which yielded the isotactic (>99% mmmm) 3,4-poly(isoprene) selectively. This is the first example of stereospecific 3,4-polymerization of isoprene.

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  • DEVELOPMENT OF MIXED-LIGAND-SUPPORTED LANTHANIDE POLYMERIZATION CATALYSTS

    Grant number:11640573  1999 - 2000

    Japan Society for the Promotion of Science  Grants-in-Aid for Scientific Research  Grant-in-Aid for Scientific Research (C)

    HOU Zhaomin

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    Grant amount:\3400000 ( Direct Cost: \3400000 )

    (1) Reactions of (C_5Me_5)_2Sm(THF)_2 with 1 equiv of K(ER) in THF gave in high yields the C_5Me_5/ER-ligated Sm(II) complexes [(C_5Me_5)Sm(THF)_m(ER)(μ-C_5Me_5)K(THF)_n]_∞ (m=0 or 1 ; n=1 or 2 ; ER=OC_6H_2^tBu_2-2,6-Me-4 (1a), OC_6H_3^iPr_2-2,6 (1b), SC_6H_2^iPr_3-2,4,6 (1c), NHC_6H_2^tBu_3-2,4,6 (1d), or N(SiMe_3)_2 (1e)), in which the "(C_5Me_5)K(THF)_n" unit acts as a neutral coordination ligand bonding to the Sm(II) center with the "C_5Me_5" part. These complexes, particularly 1a-c, showed unique reactivity toward styrene and ethylene, which can not only polymerize styrene and ethylene, but also copolymerize them into block styrene-ethylene copolymers under the presence of both monomers. Among the ER ligands, the thiolate ligand SC_6H_2^iPr_3-2,4,6 (1c) showed the highest selectivity for the block copolymerization of styrene and ethylene, while the aryloxide OC_6H_2^tBu_2-2,6-Me-4 (1a) and the silylamide N(SiMe_3)_2 (1e) gave the highest activity for the polymerization of ethylene and that of styrene, respectively.
    (2) Addition of an appropriate cocatalyst such as MMAO or AlR_3/[Ph_3C][B(C_6F_5)_4] to the samarocene complex (C_5Me_5)_2Sm(THF)_2 or (C_5Me_5)_2Sm(μ-Me)_2AlMe_2 afforded a novel catalytic system for stereospecific 1,4-cis living polymerization of butadiene and copolymerization of butadiene with styrene.
    (3) The samarium(II) bis (aryloxide) complex Sm(OAr)_2(THF)_3 (Ar=OC_6H_2^tBu_2-2,6-Me-4) showed an extremely high activity for ring-opening polymerization of ε-caprolactone and δ-valerolactone and copolymerization of ε-caprolactone with γ-butyrolactone.

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  • 異種配位子をもつ新規二価ランタノイド錯体の合成と反応

    Grant number:09740506  1997 - 1998

    日本学術振興会  科学研究費助成事業  奨励研究(A)

    侯 召民

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    Grant amount:\2000000 ( Direct Cost: \2000000 )

    異種配位子C_5Me_5/ERをもつ一連の二価サマリウム錯体[(C_5Me_5)Sm(EAr)(C_5M_5)K(THF)_2]_∞(ER=OC_6H_3^iPr_2-2,6,OC_6H_2^tBu_2-2,6-Me-4,SC_6H_2^iPr_3-2,4,6,N(SiMe_3)_2)を合成し、スチレンとエチレンの共存下でのブロック共重合に対する触媒活性を比較検討した。チオラート配位子SC_6H_2^iPr_3-2,4,6をもつ錯体は共重合に対し最も高い選択性を示し、ホモポリマーがごく少量しか生成せず、対応するブロック共重合体を選択的に与えた。アリールオキシド配位子の場合、OC_6H_3^iPr_2-2,6をもつ錯体がより立体的に嵩高いOC_6H_2^tBu_2-2,6-Me4をもつものと比べ高い反応性を示し、またスチレンモノマーの仕込み量が同じ場合ではポリスチレン含有量の高い共重合体を与えた。さらに、これらの重合反応で得られた共重合体中のポリスチレン含有量がスチレンモノマーの仕込み量の増加と共に上昇し、事実上任意に調節することかできることがわかった。一方、トリメチルシリルアミド配位子N(SiMe_3)_2をもつ錯体の場合は、同様な条件下で共重合体がほとんど得られず、ホモポリスチレンのみが生成した。このように、スチレンとエチレンの共重合において錯体のER配位子が触媒活性やポリマーの成長などに強い影響を及ぼすが明らかになった。

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  • ピナコールの炭素一炭素結合切断による金属ケチルラジカル錯体の合成と反応

    Grant number:08740530  1996

    日本学術振興会  科学研究費助成事業  奨励研究(A)

    侯 召民

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    Grant amount:\1200000 ( Direct Cost: \1200000 )

    金属ビス(トリメチルシリル)アミド(MN(SiMe_3)_2,M=Li,Na,K)を脱プロトン化剤として用い1,2-ビス(ビフェニル-2,2′-ジイル)エタン-1,2-ジオールとの反応により対応するケチルラジカル錯体を単離し、その構造をX線構造解析により明らかにした。これらの錯体の構造は金属の種類や配位子の添加量に依存する。リチウムの場合は二量体[Li(μ_2-ketyl)(HMPA)_2]_2、カリウムの場合は四量体[K(μ_3-ketyl)(HMPA)]_4[μ_2-THF]のみが単離されたが、ナトリウムの場合は一当量のHMPAを添加すると四量体[Na(μ_3-ketyl)(HMPA)]_4のみが生成し、二当量のHMPAを添加すると二量体[Na(μ_2-ketyl)(HMPA)_2]_2のみが得られた。ケチルラジカルが二量体以上の集合体として存在することが以前にESRなどの研究によって示唆されたことがあるが、それを単離して構造を決めたのは今回が初めてである。また、本研究はピナコールの炭素-炭素結合の切断によるケチルラジカル錯体の合成を実現した初めての例でもある。その他、カルシウムやサマリウム金属とフルオレノンの反応により初めてのマルチ(ケチル)錯体を単離しその構造を明らかにした。

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  • アルコキシドを配位子とする新規二価ランタノイド錯体の合成、構造及び反応性の研究

    Grant number:08220269  1996

    日本学術振興会  科学研究費助成事業  重点領域研究

    若槻 康雄, 侯 召民

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    Grant amount:\2100000 ( Direct Cost: \2100000 )

    サマリウム(II)ビスアリールオキシド(ArO)_2Sm(THF)_3(Ar=C_6H_2^tBu_2-2,6-R-4,R=H,Me,^tBu)をTHF中においてC_5Me_5Kと反応させるとArOとC_5Me_5を同時にもつSm(II)錯体[(C_5Me_5)Sm(OAr)K(C_5Me_5)(THF)2]_∞を与えた。この錯体は中心金属に“C_5Me_5K(THF)_2"が“中性配位子"として配位している極めて稀な錯体である。(C_5Me_5)_2Sm(THF)_2と一当量のArOHをトルエン中で反応させると、中性配位子を含まない混合型錯体[(C_5Me_5)Sm(μ-OAr)]_2が得られた。これらの混合型錯体をHMPAと反応させると、対応するHMPAが配位した錯体(C_5Me_5)Sm(OAr)(HMPA)_2が生成した。
    (C_5Me_5)Sm(OAr)(HMPA)_2はフルオレノンと反応すると不均化せず対応するケチル錯体(C_5Me_5)Sm(OAr)(ketyl)(HMPA)を与え、混合型配位子をもつ一電子還元剤としての有用性を示した。また、これらのアリ-オキシド配位子含有新規Sm(II)錯体はカテコールボランによるオレフィンのビドロボレーション、エチレンやスチレンなどの重合反応において(C_5Me_5)_2Sm(THF)_2の場合に見られない高い触媒活性を示した。
    その他、サマリウム金属と三当量のフルオレノンとの反応により初めてのトリス(ケチル)錯体を単離しその構造を明らかにすると共に反応性を検討した。

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  • アルコキシドを配位子とする新規二価ランタノイド錯体の合成、構造および反応性

    Grant number:07230296  1995

    日本学術振興会  科学研究費助成事業  重点領域研究

    若槻 康雄, 候 召民

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    Grant amount:\2100000 ( Direct Cost: \2100000 )

    本年度は主にアルコキシドのランタニド二価錯体の合成、ならびにケトン類との反応を検討した。二価のヨウ化サマリウムあるいはイッテリビウムとリチウムアミドの反応により二価ランタニドのアミド錯体を得、これにフェノール誘導体を加えることにより(ArO)_2Ln(THF)_2錯体合成に成功しHMPA配位体についてX-線解析により構造を明らかにした。これら錯体の溶液にベンゾフェノンを加えるとまず暗紫色を呈するが、ゆっくりと無色の結晶が析出する。Ybの場合につきこの錯体の結晶構造を明らかにした。最初観測された色をもつケチル中間体が溶媒から水素を引き抜いた後不均化したと思われる(Pn_2CHO)_2(ArO)Yb(HMPA)_2錯体であることが解った。ベンゾフェノンの代りにフルオレノンを用いると、共鳴効果によるラジカルの反応性低下のため水素引き抜きは起こらず、対応するケチルラジカル錯体(ArO)_2(kety1)Ln(THF)_3(Ln=Sm,Yb)を高収率で得ることができ、X線による単結晶構造解析を行うことができた。ケチルラジカルはケトンを用いる有機合成における重要な中間体として古くから存在が推定されていたが、結晶として構造が確認できた初めての例である。このケチル錯体に配位したTHF溶媒は配位力が弱く、結晶をヘキサン/エーテル中に溶かすとエーテル一分子の配位に変わる。同時にケチルラジカルの分子間カップリングが起こり、結果的にサマリウムのピナコラート錯体が得られ、単結晶構造解析で確認できた。このピナコラート錯体をTEFに溶かすと炭素一炭素結合の切断が起こりケチル錯体が定量的に再生することも確認した。

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  • d-fブロック遷移金属混合型錯体系の開発

    Grant number:06740519  1994

    日本学術振興会  科学研究費助成事業  奨励研究(A)

    侯 召民

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    Grant amount:\900000 ( Direct Cost: \900000 )

    d-fブロック遷移金属混合型錯体として、とくに反応性に富んでいる二価ランタノイドを含む混合型錯体について重点的に研究を行なった。
    まず、当研究室で開発したYb(II)-ベンゾフェノンジアニオン錯体[Yb(μ-η^1,η^2-OCPh_2)(HMPA)_2]_2を用いて、二当量のCpMo(CO)_3と反応させ、Yb-Mo混合型錯体の合成を試みた。この場合は、対応する二価イッテルビウム錯体Yb(HMPA)_4(μ-OCMo(CO)_2CP)_2が50%収率(Mo基準)で得られ、その構造をX線構造解析により明らかにしたが、この錯体は中心金属Yb(II)に強い電子供与力をもつHMPA配位子が配位しているため、三価のイッテウビウム錯体[Yb(HMPA)_5(μ-OCMo(CO)_2CP)][CpMo(CO)_3]_2に不均化しやすいことがわかった。
    次に、HMPA配位子をもたない二価ランタノイドアミド錯体Ln(N(SiMe_3)_2)_2(THF)_2(Ln=Sm,Yb)を用いて、d-ブロック遷移金属カルボニルヒドリドCpM(CO)_3H(M=Mo,W)との反応を行なった。これらの反応から対応する二価ランタノイド混合型錯体{Ln(THF)_n(μ,η^1-OC)_2M(CO)Cp)_2}∞(n=3,4;Ln=Sm,Yb;M=Mo,W)が高収率で得られた。X線構造解析により、これらの錯体がすべてポリマー構造を持つことが明らかになった。
    本研究で得られた混合型錯体は二価ランタノイドを含むd-fブロック遷移金属混合型錯体として数少ない例であり、新しい反応の開発に役立つことが期待される。

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  • 1.New catalysts 2.New reactions 3.New polymers

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    Grant type:Competitive

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  • 1.新規触媒 2.新反応 3.新高分子材料

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    Grant type:Competitive

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