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Highly efficient catalysts for the activation of inert substrates with the assist of synergetic interaction between base metal and metalloid

Research Project

Project/Area Number 15K21222
Research Category

Grant-in-Aid for Young Scientists (B)

Allocation TypeMulti-year Fund
Research Field Inorganic chemistry
Synthetic chemistry
Research InstitutionKyushu University

Principal Investigator

Tahara Atsushi  九州大学, 先導物質化学研究所, 助教 (50713145)

Project Period (FY) 2015-04-01 – 2018-03-31
Project Status Completed (Fiscal Year 2017)
Budget Amount *help
¥4,160,000 (Direct Cost: ¥3,200,000、Indirect Cost: ¥960,000)
Fiscal Year 2016: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Fiscal Year 2015: ¥2,080,000 (Direct Cost: ¥1,600,000、Indirect Cost: ¥480,000)
Keywords鉄 / ケイ素 / アルケンの水素化 / コバルト / 理論計算 / アルケンのヒドロシリル化 / 計算科学 / σ-CAM / 貴金属代替反応 / 金属-配位子の協同作用 / ホウ素 / 水素化 / 貴金属代替
Outline of Final Research Achievements

The purpose of the research is to replace noble-metal-catalysts for the reduction of unsaturated bonds into base-metal-catalysts. Iron complex 1, which bears Fe-Si bonds, catalyzed hydrogenation of alkenes under mild condition (1 atm of H2 at ambient temperature). Theoretical studies revealed that H-H bond is activated not on the iron center but with the assist of Fe-Si bond to afford Fe-H and Si-H bond with lower energy barrier. This system could be applied into other metals by synthesizing Ru analogues. Finally, we achieved to develop highly efficient Fe catalysts for the hydrogenation of sterically-hindered tetrasubstituted alkenes.

Report

(4 results)
  • 2017 Annual Research Report   Final Research Report ( PDF )
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (39 results)

All 2018 2017 2016 2015 Other

All Journal Article (9 results) (of which Int'l Joint Research: 1 results,  Peer Reviewed: 9 results,  Open Access: 2 results,  Acknowledgement Compliant: 2 results) Presentation (24 results) (of which Int'l Joint Research: 9 results,  Invited: 6 results) Remarks (2 results) Patent(Industrial Property Rights) (4 results) (of which Overseas: 2 results)

  • [Journal Article] Disilaruthena- and Ferracyclic Complexes Containing Isocyanide Ligands as Effective Catalysts for Hydrogenation of Unfunctionalized Sterically Hindered Alkenes2018

    • Author(s)
      Sunada, Y.; Ogushi, H.; Yamamoto, T.; Uto, S.; Sawano, M.; Tahara, A.; Tanaka, H.; Shiota, Y.; Yoshizawa, K.; Nagashima, H.
    • Journal Title

      Journal of the American Chemical Society

      Volume: 140 Issue: 11 Pages: 4119-4134

    • DOI

      10.1021/jacs.8b00812

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] σ-CAM Mechanisms for the Hydrogenation of Alkenes by cis- and trans-Disilametallacyclic Carbonyl Complexes (M = Fe, Ru, Os): Experimental and Theoretical Studies2017

    • Author(s)
      K. Miyamoto, A. Tahara, Y. Sunada, H. Tutumi, R. Inoue, H. Tanaka, Y. Shiota, K. Yoshizawa, and H. Nagashima
    • Journal Title

      Bull. Chem. Soc. Jpn.

      Volume: 99 Issue: 5 Pages: 613-626

    • DOI

      10.1246/bcsj.20170004

    • NAID

      130006770718

    • Related Report
      2017 Annual Research Report 2016 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] ベースメタルと典型元素による分子活性化の最近の動向2017

    • Author(s)
      田原 淳士
    • Journal Title

      Organometallic News

      Volume: 2 Pages: 80-80

    • Related Report
      2017 Annual Research Report 2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalyst Design of Iron Complexes2017

    • Author(s)
      Hideo Nagashima
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 90 Issue: 7 Pages: 761-775

    • DOI

      10.1246/bcsj.20170071

    • NAID

      130005773710

    • Related Report
      2017 Annual Research Report 2016 Research-status Report
    • Peer Reviewed / Open Access
  • [Journal Article] Disilametallacyclic chemistry for efficient catalysis2017

    • Author(s)
      Sunada, Y.; Nagashima, H.
    • Journal Title

      Dalton Transaction

      Volume: 46 Issue: 24 Pages: 7644-7655

    • DOI

      10.1039/c7dt01275f

    • Related Report
      2017 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Theoretical Study of the Catalytic Hydrogenation of Alkenes by a Disilaferracyclic Complex: Can the Fe-Si s-Bond-assisted Activation of H-H Bonds Allow Development of an Efficient Catalysis of Iron?2016

    • Author(s)
      A. Tahara, H. Tanaka, Y. Sunada, Y. Shiota, K. Yoshizawa, and H. Nagashima
    • Journal Title

      J. Org. Chem.

      Volume: 81 Issue: 22 Pages: 10900-10911

    • DOI

      10.1021/acs.joc.6b01961

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] アルケンのヒドロシリル化用鉄・コバルト触媒の開発2016

    • Author(s)
      永島 英夫, 真川 敦嗣, 田原 淳士, 砂田 祐輔,作田 晃司, 野田 大輔
    • Journal Title

      ケイ素化学協会誌

      Volume: 第33号 Pages: 4-13

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Non-Precious-Metal Catalytic Systems Involving Iron or Cobalt Carboxylates and Alkyl Isocyanides for Hydrosilylation of Alkenes with Hydrosiloxanes2016

    • Author(s)
      Daisuke Noda, Atsushi Tahara, Yusuke Sunada, Hideo Nagashima,
    • Journal Title

      J. Am. Chem. Soc.

      Volume: 138 Issue: 8 Pages: 2480-2483

    • DOI

      10.1021/jacs.5b11311

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Journal Article] Catalyst Design of Vaska-Type Iridium Complexes for Highly Efficient Synthesis of π-Conjugated Enamines2015

    • Author(s)
      Atsushi Tahara, Yasumitsu Miyamoto, Ryota Aoto, Keisuke Shigeta, Yuta Une, Yusuke Sunada, Hideo Nagashima,
    • Journal Title

      Organometallics

      Volume: 34 Issue: 20 Pages: 4985-4907

    • DOI

      10.1021/acs.organomet.5b00636

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] Theoretical Studies of the Catalytic Hydrogenation of Alkenes by a series of Disilametallacyclic iron and ruthenium Complexes2017

    • Author(s)
      田原淳士・田中宏昌・砂田祐輔・塩田淑仁・吉澤一成・永島英夫
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学日吉キャンパス、神奈川
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Exploration of iridium catalysts which achieves highly efficient hydrosilane reduction of carbonyl compounds2017

    • Author(s)
      宇根悠太、田原淳士、永島英夫
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学日吉キャンパス、神奈川
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Synthesis and Characterization of Donnor-Acceptor Compounds Having π-Conjugated Enamines by Iridium-catalyzed Selective Hydrosilane Reduction of Carboxamides2017

    • Author(s)
      北原いくみ、永島英夫、田原淳士
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学日吉キャンパス、神奈川
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] A Theoretical Study of the Catalytic Hydrogenation of Alkenes by Disilaruthenacyclic Complexes2017

    • Author(s)
      星香花、田原淳士、田中宏昌、砂田祐輔、塩田淑仁、吉澤一成、永島英夫
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶応大学日吉キャンパス、神奈川
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] ジシラメタラサイクル骨格を有する8族遷移金属錯体を用いたアルケンの水素化に関する理論研究2017

    • Author(s)
      田原 淳士
    • Organizer
      統合物質創成科学研究推進機構 (IRCCS) 第1回若手研究者の会
    • Related Report
      2017 Annual Research Report
    • Invited
  • [Presentation] Theoretical Studies of the Hydrogenation of Alkenes catalyzed by a Series of Disilametallacyclic Complexes which bears cis- or trans-Dicarbonyl Ligands (M = Fe, Ru, Os)2017

    • Author(s)
      田原淳士、砂田祐輔、田中宏昌、塩田淑仁、吉澤一成、永島英夫
    • Organizer
      第64回有機金属化学討論会
    • Related Report
      2017 Annual Research Report
  • [Presentation] 8族遷移金属錯体を用いた他置換アルケンの水素化に関する理論研究2017

    • Author(s)
      田原淳士、永島英夫
    • Organizer
      統合物質創製化学研究推進機構 第3回国内シンポジウム
    • Related Report
      2017 Annual Research Report
  • [Presentation] Theoretical Studies of the Catalytic Hydrogenation of Alkenes by Disilametallacyclic Complexes bearing cis- and trans-Dicarbonyl Ligands (M = Fe, Ru, Os)2017

    • Author(s)
      Atsushi Tahara, Yusuke Sunada, Hiromasa Tanaka, Yoshihito Shiota, Kazunari Yoshizawa, Hideo Nagashima
    • Organizer
      the 19th IUPAC International Symposium on Organometallic Chemistry Directed Towards Organic Synthesis (OMCOS 19)
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] Theoretical Studies of the Catalytic Hydrogenation of Alkenes by Disilametallacyclic Complexes bearing cis- and trans-Dicarbonyl Ligands (M = Fe, Ru, Os)2017

    • Author(s)
      Atsushi Tahara, Konoka Hoshi, Yusuke Sunada, Hiromasa Tanaka, Yoshihito Shiota, Kazunari Yoshizawa, Hideo Nagashima,
    • Organizer
      IRCCS-JST CREST Joint Symposium
    • Related Report
      2017 Annual Research Report
    • Int'l Joint Research
  • [Presentation] CATALYST DESIGN OF VASKA-TYPE IRIDIUM COMPLEXES FOR HIGHLY EFFICIENT SYNTHESIS OF π-CONJUGATED ENAMINES FROM CARBOXAMIDES2017

    • Author(s)
      Atsushi TAHARA, Yasumitsu MIYAMOTO, Keisuke SHIGETA, Yuta UNE, Yusuke SUNADA, Hideo NAGASHIMA
    • Organizer
      IMCE 2017
    • Place of Presentation
      Kyushu University, Fukuoka
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] ジシラルテナサイクル骨格を有するルテニウムビスイソシアニド錯体を用いた多置換アルケンの触媒的水素化反応に関する理論研究2016

    • Author(s)
      田原淳士・砂田祐輔・田中宏昌・吉澤一成・永島英夫
    • Organizer
      第20回ケイ素化学協会シンポジウム
    • Place of Presentation
      安芸グランドホテル、広島
    • Year and Date
      2016-10-07
    • Related Report
      2016 Research-status Report
  • [Presentation] シラルテナサイクル骨格を有するルテニウムビスカルボニル錯体を用いたアルケンの触媒的水素化反応に関する理論研究2016

    • Author(s)
      星香花・田原淳士・砂田祐輔・田中宏昌・吉澤一成・永島英夫
    • Organizer
      第20回ケイ素化学協会シンポジウム
    • Place of Presentation
      安芸グランドホテル、広島
    • Year and Date
      2016-10-07
    • Related Report
      2016 Research-status Report
  • [Presentation] 鉄及びコバルトカルボン酸塩とイソシアニド配位子を用いたアルケンのヒドロシリル化触媒の開発2016

    • Author(s)
      野田大輔・田原淳士・砂田祐輔・永島英夫
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学西早稲田キャンパス、東京
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] 溶媒によって安定化された単核鉄触媒を用いた原子移動ラジカル重合反応2016

    • Author(s)
      中西崇一朗・田原淳士・河村充展・砂田祐輔・永島英夫
    • Organizer
      第63回有機金属化学討論会
    • Place of Presentation
      早稲田大学西早稲田キャンパス、東京
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] A Theoretical Study of the Hydrogenation of Alkenes catalyzed by Iron Complexes bearing Disilametallacycle Moieties2016

    • Author(s)
      Atsushi Tahara
    • Organizer
      BASE METAL CATALYSIS SYMPOSIUM
    • Place of Presentation
      Princeton University, USA
    • Year and Date
      2016-09-01
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 8族遷移金属触媒を用いた還元反応に関する計算科学的考察2016

    • Author(s)
      田原 淳士
    • Organizer
      統合物質創製化学研究推進機構キックオフシンポジウム
    • Place of Presentation
      名古屋大学、愛知
    • Year and Date
      2016-06-22
    • Related Report
      2016 Research-status Report
  • [Presentation] New Iron and Ruthenium Catalysts for Hydrogenation of Alkenes2016

    • Author(s)
      Yusuke Sunada, Atsushi Tahara and Hideo Nagashima
    • Organizer
      THE 70th FUJIHARA Seminar
    • Place of Presentation
      THE LUIGANS, Fukuoka
    • Year and Date
      2016-04-17
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] 鉄触媒を用いるケイ素材料製造プロセスの最先端2016

    • Author(s)
      永島英夫
    • Organizer
      第96回日本化学会春季年会
    • Place of Presentation
      同支社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
    • Invited
  • [Presentation] イリジウム触媒を用いるアミドのヒドロシラン還元による共役系エナミンの合成:基質および触媒の構造が反応性に及ぼす影響2016

    • Author(s)
      田原淳士, 宇根悠太, 宮本保光, 重田啓介, 砂田祐輔, 永島英夫
    • Organizer
      第96回日本化学会春季年会
    • Place of Presentation
      同志社大学
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] Mechanistic Study for Alkene Hydrogenation catalyzed by Ruthenium Complexes bearing Disilametallacycle Moieties2016

    • Author(s)
      田原 淳士, 田中宏昌, 砂田祐輔, 吉澤一成, 永島英夫
    • Organizer
      The 5th International Conference on the MEXT Project of Integrated Research on Chemical Synthesis "Chemical Science for Future Societies"
    • Place of Presentation
      名古屋大学
    • Year and Date
      2016-01-29
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] A Theoretical Study of the Catalytic Hydrogenation of Alkenes by Disilametallacyclic Complexes2016

    • Author(s)
      Atsushi Tahara
    • Organizer
      JST-NTU Joint Seminar on Sustainable Synthesis and Catalysis
    • Place of Presentation
      Nanyang Technological University, Singapore
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Catalyst design of Vaska-type iridium complexes for efficient synthesis of π-conjugated enamines.2015

    • Author(s)
      Atsushi Tahara, Yusuke Sunada, Yukihiro Motoyama, Hideo Nagashima
    • Organizer
      PACIFICHEM2015
    • Place of Presentation
      Hilton Hawaiian Village
    • Year and Date
      2015-12-14
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research
  • [Presentation] Hydrosilylation of alkenes by common metal catalyst systems.2015

    • Author(s)
      Hideo Nagashima, Daisuke Noda, Yusuke Sunada, Atsushi Tahara
    • Organizer
      PACIFICHEM2015
    • Place of Presentation
      Hilton Hawaiian Village
    • Year and Date
      2015-12-14
    • Related Report
      2015 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] ジシラメタラサイクル骨格を有する鉄触媒を用いたアルケンの水素化に関する反応機構研究2015

    • Author(s)
      田原 淳士, 田中宏昌, 砂田祐輔, 吉澤一成, 永島英夫
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学
    • Year and Date
      2015-09-07
    • Related Report
      2015 Research-status Report
  • [Remarks] 鉄が生み出す新たな可能性

    • URL

      https://news.mynavi.jp/article/nanotech2018-9/

    • Related Report
      2017 Annual Research Report
  • [Remarks] http://nagashima-lab.cm.kyushu-u.ac.jp/

    • Related Report
      2016 Research-status Report
  • [Patent(Industrial Property Rights)] エナミン化合物およびその用途2017

    • Inventor(s)
      永島英夫、田原淳士、北原いくみ
    • Industrial Property Rights Holder
      永島英夫、田原淳士、北原いくみ
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2017-039057
    • Filing Date
      2017-03-02
    • Related Report
      2016 Research-status Report
  • [Patent(Industrial Property Rights)] ヒドロシリル化反応触媒2015

    • Inventor(s)
      永島英夫, 砂田祐輔, 田原淳士, 野田大輔, 作田晃司
    • Industrial Property Rights Holder
      永島英夫, 砂田祐輔, 田原淳士, 野田大輔, 作田晃司
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2015-140722
    • Filing Date
      2015-07-14
    • Related Report
      2015 Research-status Report
  • [Patent(Industrial Property Rights)] ヒドロシリル化反応触媒2015

    • Inventor(s)
      永島英夫,砂田祐輔,田原淳士,野田大輔,副島廣恵,作田晃司
    • Industrial Property Rights Holder
      永島英夫,砂田祐輔,田原淳士,野田大輔,副島廣恵,作田晃司
    • Industrial Property Rights Type
      特許
    • Filing Date
      2015-08-12
    • Related Report
      2015 Research-status Report
    • Overseas
  • [Patent(Industrial Property Rights)] ヒドロシリル化反応触媒2015

    • Inventor(s)
      永島英夫,砂田祐輔,田原淳士,野田大輔,副島廣恵,作田晃司
    • Industrial Property Rights Holder
      永島英夫,砂田祐輔,田原淳士,野田大輔,副島廣恵,作田晃司
    • Industrial Property Rights Type
      特許
    • Filing Date
      2015-08-12
    • Related Report
      2015 Research-status Report
    • Overseas

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Published: 2015-04-16   Modified: 2019-03-29  

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