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Syntheses and Reactivities of Silanimine- and Phosphasilene-coordinated Electron-deficient Complexes

Research Project

Project/Area Number 15K05443
Research Category

Grant-in-Aid for Scientific Research (C)

Allocation TypeMulti-year Fund
Section一般
Research Field Inorganic chemistry
Research InstitutionHirosaki University

Principal Investigator

Okazaki Masaaki  弘前大学, 理工学研究科, 教授 (20292203)

Co-Investigator(Kenkyū-buntansha) 太田 俊  弘前大学, 理工学研究科, 助教 (20733132)
Project Period (FY) 2015-04-01 – 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 2017: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000)
Fiscal Year 2016: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000)
Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
Keywordsシライミン錯体 / ホスファシレン錯体 / 電子欠損錯体 / 反応場構築 / ルイス酸 / カルベニウムイオン / メタラサイクル / シライミン / ホスファシレン / 有機金属錯体 / 小分子活性化 / 有機金属化学
Outline of Final Research Achievements

Reaction of an electron-deficient silanimine-coordinated titanium complex with ketones yielded the insertion products between the titanium-silicon bond. In the reaction with 1,3-dimethyl-2-imidazolidinone, the unusual cleavage of the carbon-oxygen double bond has been achieved. We also synthesized the silanimine-bridged diruthenium complex, which reacted with carbon monoxide and isocyanides to give the products. The reaction can be explained by assuming 1,2-H-shift of the bridging hydrogen atom to the nitrogen atom and the Si-H reductive elimination. These reactions are potentially applicable to the coupling between hydroamine and dihydrosilane. The iridium complexes possessing phosphasilene and silanethione moieties were synthesized and uniquely characterized by X-ray diffraction study. Theses complexes were highly reactive toward polarized small molecules.

Academic Significance and Societal Importance of the Research Achievements

これまで遷移金属錯体触媒の多くでは、一連の反応は金属中心で進行することが仮定され、分子設計がなされてきた。一方、元素戦略的な観点からいうと、希少な遷移金属に頼ることなく、クラーク数の大きい主要族元素を反応活性点として触媒を設計できれば、持続可能な社会構築に寄与できる。本研究成果は、ケイ素、窒素、リン、硫黄、炭素といった主要族元素を用いて、将来的に触媒へと展開可能な反応場の構築を行った点で、学術的および社会的な意義は大きいといえる。

Report

(5 results)
  • 2018 Annual Research Report   Final Research Report ( PDF )
  • 2017 Research-status Report
  • 2016 Research-status Report
  • 2015 Research-status Report
  • Research Products

    (42 results)

All 2018 2017 2016 2015 Other

All Journal Article (8 results) (of which Peer Reviewed: 8 results,  Acknowledgement Compliant: 2 results,  Open Access: 1 results) Presentation (29 results) (of which Int'l Joint Research: 1 results,  Invited: 1 results) Book (1 results) Remarks (4 results)

  • [Journal Article] Synthesis and photophysical properties of azuleno[1′,2′:4,5]pyrrolo[2,1-b]quinazoline-6,14-diones: Azulene analogs of tryptanthrin2018

    • Author(s)
      Chieko Kogawa, Asuka Fujiwara, Ryuta Sekiguchi, Taku Shoji, Jun Kawakami, Masaaki Okazaki, Shunji Ito*
    • Journal Title

      Tetrahedron

      Volume: 74 Issue: 49 Pages: 7018-7029

    • DOI

      10.1016/j.tet.2018.10.020

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Ethylene polymerization and ethylene/1-octene copolymerization with a titanium complex supported by a bis(indolyl) ligand2018

    • Author(s)
      Ohta Shun、Kasai Yuki、Toda Tomoyuki、Nishii Kei、Okazaki Masaaki
    • Journal Title

      Polymer Journal

      Volume: 51 Issue: 3 Pages: 345-349

    • DOI

      10.1038/s41428-018-0124-9

    • NAID

      40021935781

    • Related Report
      2018 Annual Research Report
    • Peer Reviewed
  • [Journal Article] Transformation of Tertiary Amines at a Cationic [CCH] Subunit Stabilized by Coordination with a Tetrairon Core2018

    • Author(s)
      Masakazu Nishiya, Ryo Funada, Shun Ohta, Masaaki Okazaki
    • Journal Title

      chemistry letters

      Volume: 47 Issue: 1 Pages: 48-50

    • DOI

      10.1246/cl.170913

    • NAID

      130006302081

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Stereochemical Correction and Total Structure of Roridin J2017

    • Author(s)
      Manami Matsumoto, Atsushi Ito, Akio Tonouchi, Masaaki Okazaki, Masaru Hashimoto
    • Journal Title

      Tetrahedron

      Volume: 73 Issue: 36 Pages: 5430-5435

    • DOI

      10.1016/j.tet.2017.07.048

    • Related Report
      2017 Research-status Report
    • Peer Reviewed
  • [Journal Article] Impact of ligands and media on the structure and properties of biological and biomimetic iron-sulfur clusters2017

    • Author(s)
      Shun Ohta and Yasuhiro Ohki
    • Journal Title

      Coordination Chemistry Reviews

      Volume: 338 Pages: 207-225

    • DOI

      10.1016/j.ccr.2017.02.018

    • NAID

      120006305605

    • Related Report
      2016 Research-status Report
    • Peer Reviewed
  • [Journal Article] Directed ortho-C-H Silylation Coupled with trans-Selective Hydrogenation of Arylalkynes Catalyzed by Ruthenium Complexes of a Xanthene-Based Si,O,Si-Chelate Ligand, “Xantsil”2016

    • Author(s)
      Takashi Komuro, Takeo Kitano, Nobukazu Yamahira, Keisuke Ohta, Satoshi Okawara, Nathalie Mager, Masaaki Okazaki, Hiromi Tobita
    • Journal Title

      Organometallics

      Volume: 印刷中 Issue: 9 Pages: 1209-1217

    • DOI

      10.1021/acs.organomet.5b01013

    • Related Report
      2016 Research-status Report
    • Peer Reviewed / Acknowledgement Compliant
  • [Journal Article] Activation of Isocyanides and Hydrosilanes by a Cationic [CCH] Subunit in a Tetrairon-Tetracarbon Cluster2016

    • Author(s)
      Wataru Taniwaki, Shun Ohta, and Masaaki Okazaki
    • Journal Title

      Bulletin of the Chemical Society of Japan

      Volume: 89 Issue: 1 Pages: 11-19

    • DOI

      10.1246/bcsj.20150289

    • NAID

      130005119453

    • Related Report
      2015 Research-status Report
    • Peer Reviewed / Open Access / Acknowledgement Compliant
  • [Journal Article] Isolation, absolute structures, and biological properties of cyclohelminthols I-IV from Helminthosporium velutinum yone962016

    • Author(s)
      Yuna Honmura, Shota Uesugi, Hayato Maeda, Kazuaki Tanaka, Tatsuo Nehira, Ken-ichi Kimura, Masaaki Okazaki, Masaru Hashimot
    • Journal Title

      Tetrahedron

      Volume: 72 Issue: 10 Pages: 1400-1405

    • DOI

      10.1016/j.tet.2016.01.036

    • Related Report
      2015 Research-status Report
    • Peer Reviewed
  • [Presentation] ビス(インドリル)配位子を持つ4族遷移金属ジアミド錯体の合成と性質2018

    • Author(s)
      竹中亜門, 新林雅也, 岡崎雅明, 太田俊
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] トリフラート配位子を有するハーフサンドイッチ型4族遷移金属ヒドロシリルアミド錯体の合成、構造および性質2018

    • Author(s)
      干場有記, 太田俊, 岡崎雅明
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] ビス(インドリル)配位子に保護されたチタンジクロリド錯体の合成とマグネシウムによる還元反応2018

    • Author(s)
      三浦也美, 岡崎雅明, 太田俊
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] シライミンが架橋配位したルテニウム二核錯体とイソシアニド類との反応2018

    • Author(s)
      山崎崇平, 松平将司, 太田俊, 岡崎雅明
    • Organizer
      錯体化学会第68回討論会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Pyramidal Coordination of an Amido Nitrogen in Bis(indolyl) Ligands toward Group IV Transition Metals2018

    • Author(s)
      Shun Ohta, Masaya Shimbayashi, Amon Takenaka, Yuki Kasai, Tomoyuki Toda, Kei Nishii, Ryo Miyamoto, Masaaki Okazaki
    • Organizer
      43rd International Conference on Coordination Chemistry (ICCC2018)
    • Related Report
      2018 Annual Research Report
    • Int'l Joint Research
  • [Presentation] ビスベンゾイミダゾール配位金属ジクロリド錯体の合成と分子間N-H-Cl結合を利用した集積化2018

    • Author(s)
      岩渕由理香, 岡崎雅明, 太田俊
    • Organizer
      第8回CSJ化学フェスタ2018
    • Related Report
      2018 Annual Research Report
  • [Presentation] ジルコニウムビスインドリル錯体における配位構造変化の挙動についての理論的研究2018

    • Author(s)
      宮本量, 竹中亜門, 岡崎雅明, 太田俊
    • Organizer
      日本コンピュータ化学会2018秋季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] カチオン性ハーフサンドイッチ型4族遷移金属ヒドロシリルアミド錯体の合成、構造および性質2018

    • Author(s)
      干場有記, 太田俊, 岡崎雅明
    • Organizer
      日本化学会第99春季年会
    • Related Report
      2018 Annual Research Report
  • [Presentation] Side-on型シランチオン配位イリジウム錯体と硫黄単体との反応:硫黄挿入生成物のキャラクタリゼーション2018

    • Author(s)
      大谷隆介, 太田俊, 岡崎雅明
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] ビス(インドリル)配位4族遷移金属ジアミド錯体の合成、構造および触媒的ヒドロアミノ化反応への利用2018

    • Author(s)
      新林雅也, 竹中亜門, 岡崎雅明, 太田 俊
    • Organizer
      日本化学会第98春季年会
    • Related Report
      2017 Research-status Report
  • [Presentation] ペンタメチルシクロペンタジエニルを支持配位子としてもつ4族遷移金属ヒドロシリルアミド錯体の合成と反応性2017

    • Author(s)
      畑中鴻希、太田俊、岡崎 雅明
    • 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
    • Year and Date
      2017-03-16
    • Related Report
      2016 Research-status Report
  • [Presentation] 陽イオン性ルテニウム多核錯体を用いたニトリルおよびイソニトリルの炭素-窒素三重結合の開裂反応2017

    • Author(s)
      池田舞, 柴山伸, 太田俊, 岡崎雅明
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] side-on型シランチオン配位イリジウム錯体と小分子との反応2017

    • Author(s)
      大谷隆介, 谷脇旦,太田俊, 岡崎雅明
    • Organizer
      錯体化学会第67回討論会
    • Related Report
      2017 Research-status Report
  • [Presentation] Activation of small organic molecules by an iridium complex possessing a side-on-bound phosphasilene ligand2017

    • Author(s)
      Yuuya Terauchi, Tetsuaki Oguro, Shun Ohta, Masaaki Okazaki
    • Organizer
      平成29年度化学系学協会東北大会
    • Related Report
      2017 Research-status Report
  • [Presentation] Reactivity of a silanimine-bridged dinuclear ruthenium complex toward isocyanides2017

    • Author(s)
      Shuhei Yamazaki, Masashi Matsudaira, Shun Ohta, Masaaki Okazaki
    • Organizer
      平成29年度化学系学協会東北大会
    • Related Report
      2017 Research-status Report
  • [Presentation] An attempt to improve the reactivity of a silanimine-titanium complex and metallacycles derived from the insertion reactions with substrates through the construction of a vacant site at the titanium center2017

    • Author(s)
      Yuuki Hoshiba, Shun Ohta, Masaaki Okazaki
    • Organizer
      平成29年度化学系学協会東北大会
    • Related Report
      2017 Research-status Report
  • [Presentation] Activation of tertiary amines by cationic haloacetylene-coordinated tetrairon clusters2017

    • Author(s)
      Ryo Funada, Masakazu Nishiya, Shun Ohta, Masaaki Okazaki
    • Organizer
      平成29年度化学系学協会東北大会
    • Related Report
      2017 Research-status Report
  • [Presentation] ビスインドリル配位子を持つチタン錯体によるエチレン重合活性2017

    • Author(s)
      葛西侑毅, 戸田智之, 西井圭, 岡崎雅明, 太田俊
    • Organizer
      第66回高分子学会年次大会
    • Related Report
      2017 Research-status Report
  • [Presentation] アセチレン水素のヨウ素化を経由したビス(アセチレン)四鉄クラスターの多点官能基化2016

    • Author(s)
      居倉捷人,太田俊,岡崎雅明
    • Organizer
      第6回CSJ化学フェスタ2016
    • Place of Presentation
      タワーホール船堀(東京都江戸川区)
    • Year and Date
      2016-11-14
    • Related Report
      2016 Research-status Report
  • [Presentation] Activation of Carbon-Nitrogen Triple Bond of Nitriles by Cationic Polynuclear Ruthenium Clusters2016

    • Author(s)
      Mai Ikeda, Satoshi Kaneko, Yuhei Tsukahara, Shun Ohta, and Masaaki Okazaki
    • 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
    • Year and Date
      2016-09-14
    • Related Report
      2016 Research-status Report
  • [Presentation] Synthesis, Structure, and Reactivity of an Iridium Complex Carrying a Side-On-Bound Phosphasilene Ligand2016

    • Author(s)
      Yuya Terauchi, Tetsuaki Oguro, Shun Ohta, Masaaki Okazaki
    • Organizer
      錯体化学会第66回討論会
    • Place of Presentation
      福岡大学七隈キャンパス
    • Year and Date
      2016-09-10
    • Related Report
      2016 Research-status Report
  • [Presentation] ケイ素を含む三員環メタラサイクルの合成と反応性2016

    • Author(s)
      太田俊
    • Organizer
      第33回無機・分析化学コロキウム
    • Place of Presentation
      東北大学川渡共同セミナーセンター
    • Year and Date
      2016-06-03
    • Related Report
      2016 Research-status Report
    • Invited
  • [Presentation] ハーフサンドイッチ型チタンシライミン錯体とベンゾフェノン 類との反応と生成物の異性化2016

    • Author(s)
      大谷隆介、太田俊、岡崎雅明
    • Organizer
      日本化学会第96春季年会(2016)
    • Place of Presentation
      同志社大学京田辺キャンパス(京都府京田辺市)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] 陽イオン性イリジウム(I)錯体とリチウムヒドロシランチオラー トとの反応によるシランチオン配位イリジウム錯体の合成、構造およ び反応性2016

    • Author(s)
      谷脇 旦、太田 俊、岡崎雅明
    • Organizer
      日本化学会第96春季年会(2016)
    • Place of Presentation
      同志社大学京田辺キャンパス(京都府京田辺市)
    • Year and Date
      2016-03-24
    • Related Report
      2015 Research-status Report
  • [Presentation] 四鉄上に配位安定化した高活性陽イオン炭素種によるハロゲン化アルキルおよび有機ケイ素化合物の活性化2015

    • Author(s)
      谷脇旦,太田俊,岡崎雅明
    • Organizer
      第5回CSJ化学フェスタ2015
    • Place of Presentation
      タワーホール船堀(東京都)
    • Year and Date
      2015-10-13
    • Related Report
      2015 Research-status Report
  • [Presentation] Themal reactions of a bis(amido)diruthenium complex with small organic molecules. Structures of the products2015

    • Author(s)
      松平将司,岡崎雅明
    • Organizer
      平成27年度化学系学協会東北大会
    • Place of Presentation
      弘前大学文京キャンパス(青森県弘前市)
    • Year and Date
      2015-09-12
    • Related Report
      2015 Research-status Report
  • [Presentation] Reactivity of a Coordinatively Unsaturated Silanimine Complex of Titanium toward Unsaturated Organic Compounds2015

    • Author(s)
      畑中鴻希,蝦名祥哉,太田俊,岡崎雅明
    • Organizer
      平成27年度化学系学協会東北大会
    • Place of Presentation
      弘前大学文京キャンパス(青森県弘前市)
    • Year and Date
      2015-09-12
    • Related Report
      2015 Research-status Report
  • [Presentation] Synthesis and Reactivities of Half-Sandwich-Type Group 4 Metal Complexes Possessing a Silanimine Ligand2015

    • Author(s)
      Hiroki Hatanaka, Shoya Ebina, Ryusuke Ohtani, Shun Ohta, Masaaki Okazaki
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学千里山キャンパス(大阪府吹田市)
    • Year and Date
      2015-09-07
    • Related Report
      2015 Research-status Report
  • [Presentation] Synthesis of Phosphasilene-Coordinated Iridium Complexes by the Reactions of Vaska–Type Complexes with Lithium (Hydrosilyl)phosphide2015

    • Author(s)
      Tetsuaki Oguro, Yuya Terauchi, ○Shun Ohta, and Masaaki Okazaki
    • Organizer
      第62回有機金属化学討論会
    • Place of Presentation
      関西大学千里山キャンパス(大阪府吹田市)
    • Year and Date
      2015-09-07
    • Related Report
      2015 Research-status Report
  • [Book] 基本無機化学第3版2016

    • Author(s)
      荻野博、飛田博実、岡崎雅明
    • Total Pages
      358
    • Publisher
      東京化学同人
    • Related Report
      2016 Research-status Report
  • [Remarks] 弘前大学大学院理工学研究科岡﨑研究室

    • URL

      http://www.st.hirosaki-u.ac.jp/~inorglab/okazaki/index.html

    • Related Report
      2018 Annual Research Report
  • [Remarks] 弘前大学理工学研究科岡崎研究室

    • URL

      http://www.st.hirosaki-u.ac.jp/~inorglab/okazaki/

    • Related Report
      2017 Research-status Report
  • [Remarks] 弘前大学大学院理工学研究科岡崎研究室

    • URL

      http://www.st.hirosaki-u.ac.jp/~inorglab/okazaki/index.html

    • Related Report
      2016 Research-status Report
  • [Remarks] 弘前大学大学院理工学研究科理工学部物質創成化学科岡崎・太田研究室

    • URL

      http://www.st.hirosaki-u.ac.jp/~inorglab/okazaki/index.html

    • Related Report
      2015 Research-status Report

URL: 

Published: 2015-04-16   Modified: 2020-03-30  

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