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Development of catalytic hydrogenation using thiolate iron complexes stabilized by metallacycles

Research Project

Project/Area Number 16K05729
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionKanagawa University (2018)
Osaka City University (2016-2017)

Principal Investigator

Hirotsu Masakazu  神奈川大学, 理学部, 教授 (30312903)

Project Period (FY) 2016-04-01 – 2019-03-31
Project Status Completed (Fiscal Year 2018)
Budget Amount *help
¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000)
Fiscal Year 2018: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2016: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsチオラート / 鉄錯体 / メタラサイクル / チオフェン誘導体 / 光反応 / 一酸化炭素放出 / ヒドリド錯体 / 水素分子活性化 / 水素化 / イソシアニド錯体 / 触媒
Outline of Final Research Achievements

N,C,S-pincer iron(III) carbonyl complexes with two phosphorus ligands were synthesized, and the CO releasing properties induced by visible to near-IR light were investigated. Iron complexes of S,N,C,S-tetradentate ligands were synthesized by introducing a pendant thioether arm, which is reversibly replaced by CO. Hydride iron complexes were detected in the reaction of diphosphine-bridged diiron thiolate complexes with dihydrogen. Iron carbonyl complexes stabilized by metallacycles were synthesized from quinolyl-substituted thiophene derivatives.

Academic Significance and Societal Importance of the Research Achievements

地球上に豊富に存在し、環境適合性の高い鉄を利用した機能性物質の開発は、持続可能な社会を築くうえで有用である。自然界の酸化還元酵素では鉄-硫黄骨格が重要な役割を果たしているが、その仕組みを人工触媒に組み込むことは非常に難しい。本研究では、メタラサイクルで安定化したチオラート鉄錯体を多く開発しており、酵素に見られる鉄-硫黄骨格の特徴を生かした触媒開発への展開が期待できる。

Report

(4 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • Research Products

    (38 results)

All 2019 2018 2017 2016 Other

All Journal Article (5 results) (of which Peer Reviewed: 4 results,  Acknowledgement Compliant: 1 results) Presentation (31 results) (of which Int'l Joint Research: 8 results,  Invited: 4 results) Remarks (1 results) Patent(Industrial Property Rights) (1 results)

  • [Journal Article] CO Release from N,C,S-Pincer Iron(III) Carbonyl Complexes Induced by Visible-to-NIR Light Irradiation: Mechanistic Insight into Effects of Axial Phosphorus Ligands2018

    • Author(s)
      Nakae Toyotaka、Hirotsu Masakazu、Nakajima Hiroshi
    • Journal Title

      Inorganic Chemistry

      Volume: 57 Issue: 14 Pages: 8615-8626

    • DOI

      10.1021/acs.inorgchem.8b01407

    • NAID

      120006649313

    • URL

      https://ocu-omu.repo.nii.ac.jp/records/2019894

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] 近赤外光応答性一酸化炭素放出物質の開発─ガス医療への応用を目指して─2018

    • Author(s)
      中島洋, 廣津昌和
    • Journal Title

      化学工業

      Volume: 69 Pages: 595-601

    • Related Report
      2018 Annual Research Report
  • [Journal Article] Iron carbonyl complexes of N,C,S-pincer ligands with a pendant thioether arm: Synthesis, structures and reactivity2018

    • Author(s)
      Masakazu Hirotsu, Kiyokazu Santo, Yui Tanaka, Isamu Kinoshita
    • Journal Title

      Polyhedron

      Volume: 143 Pages: 201-208

    • DOI

      10.1016/j.poly.2017.10.014

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Carbon-Sulfur Bond Cleavage Reactions of Quinolyl-Substituted Thiophenes with Iron Carbonyls2017

    • Author(s)
      Takumi Matsunaga, Isamu Kinoshita, Masakazu Hirotsu
    • Journal Title

      Organometallics

      Volume: 36 Issue: 11 Pages: 2228-2236

    • DOI

      10.1021/acs.organomet.7b00280

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Visible-light-induced release of CO by thiolate iron(III) carbonyl complexes bearing N,C,S-pincer ligands2016

    • Author(s)
      Toyotaka Nakae, Masakazu Hirotsu, Shigetoshi Aono, Hiroshi Nakajima
    • Journal Title

      Dalton Trans.

      Volume: 45 Issue: 41 Pages: 16153-16156

    • DOI

      10.1039/c6dt03399g

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Presentation] Synthesis and Properties of N,C,S-Pincer Iron Carbonyl Complexes Bearing a Quinolyl Group2019

    • Author(s)
      Masakazu Hirotsu, Kotomi Nakazawa
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Incorporation Reaction into a Ferritin Mutant in Organic Solvent2019

    • Author(s)
      Tatsuya Kusumoto, Masakazu Hirotsu, Takanori Nishioka, Hiroshi Nakajima
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 配位子にプロトン化部位を持つCO放出鉄錯体の合成2019

    • Author(s)
      田中聖哉, 廣津昌和, 西岡孝訓, 中島洋
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Reactivity of iron carbonyl complexes of N,C,S-pincer ligands with a pendant thioether arm2018

    • Author(s)
      Masakazu Hirotsu, Yui Tanaka, Yusuke Nakamura, Toyotaka Nakae, Hiroshi Nakajima
    • Organizer
      第43回錯体化学国際会議
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] NIR responsive CO releasing iron complex aiming at biological use2018

    • Author(s)
      Hiroshi Nakajima, Masakazu Hirotsu, Toyotaka Nakae, Tatsuya Kusumoto
    • Organizer
      第43回錯体化学国際会議
    • Related Report
      2018 Annual Research Report
  • [Presentation] 生体適合性の高いCORMを目指したCO放出錯体の合成とフェリチンとの複合化2018

    • Author(s)
      楠本竜也, 中島洋, 廣津昌和, 中江豊崇
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] 生体適合性の高いCORMを目指したCO放出錯体の合成とフェリチンとの複合化2018

    • Author(s)
      楠本竜也, 中江豊崇, 西岡孝訓, 廣津昌和, 中島洋
    • Organizer
      第45回生体分子科学討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Photoreactivity of Thiolate Iron Metallacyclic Complexes Derived from Functionalized Thiophenes2018

    • Author(s)
      Masakazu Hirotsu
    • Organizer
      The 2nd International Symposium on Coordination Ionic Compounds
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research / Invited
  • [Presentation] Effect of Axial Phosphorus Ligands on Visible-Light-Induced CO-Release Properties of N,C,S-Pincer Iron(III) Complexes2017

    • Author(s)
      Toyotaka Nakae, Masakazu Hirotsu, Hiroshi Nakajima
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学 日吉キャンパス(神奈川県・横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] Synthesis of π-Bridged Thiolate Iron Carbonyl Complexes by Using Thiophene Derivatives2017

    • Author(s)
      Masakazu Hirotsu, Yukari Ishimoto, Hiroshi Nakajima
    • Organizer
      日本化学会第97春季年会
    • Place of Presentation
      慶應義塾大学 日吉キャンパス(神奈川県・横浜市)
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 光応答性CO放出錯体の合成とタンパク質との複合化2017

    • Author(s)
      楠本竜也, 中島洋, 廣津昌和, 中江豊崇
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] チオフェン誘導体を用いたπ架橋チオラート鉄カルボニル錯体の合成2017

    • Author(s)
      石本有佳梨, 中島洋, 廣津昌和
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] かさ高い置換基をもつチオラート鉄メタラサイクル錯体の合成と反応2017

    • Author(s)
      中村佳輔, 中島洋, 廣津昌和
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 生体内での利用を目指した光応答性一酸化炭素放出鉄錯体の開発2017

    • Author(s)
      中江豊崇, 廣津昌和, 中島洋
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] チオフェン誘導体を用いたπ架橋チオラート鉄カルボニル錯体の合成2017

    • Author(s)
      石本有佳梨, 中島洋, 廣津昌和
    • Organizer
      先端錯体工学研究会2017年度年会
    • Related Report
      2017 Research-status Report
  • [Presentation] 鉄(III)カルボニル錯体を利用した長波長光で誘起可能な一酸化炭素放出分子の開発2017

    • Author(s)
      中江豊崇, 廣津昌和, 中島洋
    • Organizer
      先端錯体工学研究会2017年度年会
    • Related Report
      2017 Research-status Report
  • [Presentation] Thiolate Iron Carbonyl Complexes of N,C,S-Tridentate Ligands Derived from Thiophenes with N-Donor Groups2017

    • Author(s)
      Masakazu Hirotsu
    • Organizer
      International Symposium on Pure & Applied Chemistry (ISPAC) 2017
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] Development of Carbon-Monoxide-Releasing Iron Carbonyl Complexes with an N,C,S-Tridentate Ligand Induced by Light in the Biotransparent Range2017

    • Author(s)
      中江豊崇, 廣津昌和, 中島洋
    • Organizer
      第27回金属の関与する生体関連反応シンポジウム
    • Related Report
      2017 Research-status Report
  • [Presentation] 生体透過性の高い光により励起可能な一酸化炭素放出鉄カルボニ錯開発を目指して2017

    • Author(s)
      中江豊崇, 廣津昌和, 中島洋
    • Organizer
      第44回生体分子科学討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] 生体透過性の高い光に応答して一酸化炭素を放出する鉄(III)カルボニル錯体の開発2017

    • Author(s)
      中江豊崇, 廣津昌和, 中島洋
    • Organizer
      第7回CSJ化学フェスタ
    • Related Report
      2017 Research-status Report
  • [Presentation] Synthesis of Thiophene-Bridged Iron Carbonyl Complexes Derived from Quinolyl-Substituted Thiophenes2017

    • Author(s)
      Yukari Ishimoto, Hiroshi Nakajima, Masakazu Hirotsu
    • Organizer
      The 24th International SPACC Symposium
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Development of iron-based CO-releasing molecules inducible by longer wavelength light2017

    • Author(s)
      Toyotaka Nakae, Masakazu Hirotsu, Hiroshi Nakajima
    • Organizer
      The 24th International SPACC Symposium
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research
  • [Presentation] Reactivity and Redox Properties of Thiolate Iron Metallacyclic Complexes Derived from Functionalized Thiophenes2017

    • Author(s)
      Masakazu Hirotsu
    • Organizer
      The 2nd International RINS Symposium
    • Related Report
      2017 Research-status Report
    • Int'l Joint Research / Invited
  • [Presentation] チオフェン類から誘導されるレドックス活性チオラート配位子をもつ鉄錯体の合成と性質2016

    • Author(s)
      廣津昌和, 松永拓海, 中島洋
    • 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(東京都・新宿区)
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] Visible-light-induced CO release of N,C,S-pincer iron(III) carbonyl complexes2016

    • Author(s)
      Toyotaka Nakae, Masakazu Hirotsu, Hiroshi Nakajima
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Research-status Report
  • [Presentation] チオエーテル側鎖をもつN,C,S-三座シッフ塩基鉄カルボニル錯体の反応性2016

    • Author(s)
      田中優衣, 廣津昌和, 中島洋
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Research-status Report
  • [Presentation] チオラートおよびジホスフィン架橋配位子をもつ二核鉄錯体の合成と反応性2016

    • Author(s)
      村田千智, 廣津昌和, 中島洋
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学(福岡県・福岡市)
    • Year and Date
      2016-09-10
    • Related Report
      2016 Research-status Report
  • [Presentation] Water-Soluble and Visible-Light-Responsive CO-Releasing Iron(III) Carbonyl Complex2016

    • Author(s)
      Toyotaka Nakae, Masashi Kubota, Masakazu Hirotsu, Hiroshi Nakajima
    • Organizer
      OCUIC-2016 Osaka City University International Conference
    • Place of Presentation
      大阪市立大学(大阪府・大阪市)
    • Year and Date
      2016-08-31
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research
  • [Presentation] Synthesis of a water-soluble iron(III) carbonyl complex -Possible use as a biocompatible CO releaser responsive to visible-light-2016

    • Author(s)
      中江豊崇, 久保田真史, 廣津昌和, 中島洋
    • Organizer
      第26回金属の関与する生体関連反応シンポジウム
    • Place of Presentation
      北海道大学(北海道・札幌市)
    • Year and Date
      2016-06-17
    • Related Report
      2016 Research-status Report
  • [Presentation] 水素発生触媒能を有する水溶性コバルト錯体の開発および光水素発生系への適用2016

    • Author(s)
      佐納惇平, 廣津昌和, 中島洋
    • Organizer
      第5回JACI/GSCシンポジウム
    • Place of Presentation
      ANAクラウンプラザホテル神戸(兵庫県・神戸市)
    • Year and Date
      2016-06-02
    • Related Report
      2016 Research-status Report
  • [Presentation] Iron Complexes with Redox-Active Thiolate Ligands Derived from Thiophenes2016

    • Author(s)
      Masakazu Hirotsu
    • Organizer
      RIIS Symposium, Cooperative Symposium among Universities of Toulouse, Copenhagen, and Okayama
    • Place of Presentation
      岡山大学(岡山県・岡山市)
    • Related Report
      2016 Research-status Report
    • Int'l Joint Research / Invited
  • [Remarks] 神奈川大学理学部化学科 廣津研究室

    • URL

      https://www.sci.kanagawa-u.ac.jp/chem/hirotsu/index.html

    • Related Report
      2018 Annual Research Report
  • [Patent(Industrial Property Rights)] 一酸化炭素放出分子2017

    • Inventor(s)
      中江豊崇, 廣津昌和, 中島洋
    • Industrial Property Rights Holder
      大阪市立大学
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      2017-038424
    • Filing Date
      2017-03-01
    • Related Report
      2016 Research-status Report

URL: 

Published: 2016-04-21   Modified: 2020-03-30  

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