遷移金属と硫黄がともに関わる結合活性化反応と分子変換

• Project Area: Molecule Activation Directed toward Straightforward Synthesis
• Project/Area Number: 25105725
• Research Category: Grant-in-Aid for Scientific Research on Innovative Areas (Research in a proposed research area)
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Nagoya University
• Principal Investigator: 大木 靖弘 名古屋大学, 理学(系)研究科(研究院), 准教授 (10324394)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥6,240,000 (Direct Cost: ¥4,800,000、Indirect Cost: ¥1,440,000); Fiscal Year 2014: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000); Fiscal Year 2013: ¥3,120,000 (Direct Cost: ¥2,400,000、Indirect Cost: ¥720,000)
• Keywords: ルテニウム / チオラート / ヘテロリシス / ヒドロシラン / 配位不飽和錯体 / 硫黄 / ヒドロボラン

Outline of Annual Research Achievements

本研究では、かさ高いチオラートをテザー型に配位させ、外部基質と反応し易いようRu-S部位を配置するとともに硫黄原子が金属を架橋することを抑制した、配位不飽和なカチオン性ルテニウム錯体を用い、そのRu-S部位による結合活性化（ヘテロリシス）反応を、分子変換反応へと応用した。

(1) エーテル類のC-O結合切断反応
Et2OあるいはTHFにルテニウム錯体を溶解させ、そこへEt3SiHを加えたところ、溶媒のC-O結合を切断してRu-H／S-C結合を持つ錯体が生成した。この反応に基づいて、さらに触媒的なC-O結合切断反応への展開を試みた。Et2Oを溶媒兼試薬として用い、シラン類に対して触媒量(2 mol%)のルテニウム錯体を溶解させ、HSiMe2Phを加えて90 °Cで12時間撹拌したところ、NMR収率80 %でEtOSiMe2Phが生成した。このとき、HSiMe2Phは99%以上転化されていることも確認した。
(2) 芳香環C-H結合の分子内シリル化によるジベンゾシロールの合成
Ru-H／S-Si結合を持つ錯体をシリルカチオン等価体と見なした、Friedel-Crafts型の脱水素カップリング反応は、インドール等の電子リッチなへテロ芳香環でなければ進行しないが、分子内反応であれば、ベンゼン環でも進行することを見出した。ルテニウム錯体(2 mol%)存在下、HSiMe2(biphenyl)を加え80 °Cで12時間反応させると、ジベンゾシロールが生成することが、NMRおよび質量分析から明らかになった。

Research Progress Status

26年度が最終年度であるため、記入しない。

Strategy for Future Research Activity

26年度が最終年度であるため、記入しない。

Research Products

• [Journal Article] Synthesis of V/Fe/S Clusters Using Vanadium(III)Thiolate Complexes Bearing a Phenoxide-Based Tridentate Ligand (2014)
  • Author(s): N. Taniyama, Y. Ohki, K. Tatsumi
  • Journal Title: Inorg. Chem. Volume: 53 Issue: 11 Pages: 5438-5446
  • DOI: 10.1021/ic4030603
  • Peer Reviewed
• [Journal Article] A Convenient Route to Synthetic Analogues of the Oxidized Form of High-Potential Iron-Sulfur Proteins (2014)
  • Author(s): K. Tanifuji, N. Yamada, T. Tajima, T. Sasamori, N. Tokitoh, T. Matsuo, K. Tamao, Y. Ohki, K. Tatsumi
  • Journal Title: Inorganic Chemistry Volume: 53 Issue: 8 Pages: 4000-4009
  • DOI: 10.1021/ic402890k
  • Peer Reviewed
• [Journal Article] Synthetic Analogues of the Active Sites of Nitrogenase and [NiFe] Hydrogenase (2014)
  • Author(s): Y. Ohki
  • Journal Title: Bulletin of the Chemical Society of Japan Volume: 87 Issue: 1 Pages: 1-19
  • DOI: 10.1246/bcsj.20130207
  • NAID: 130004153267
  • Peer Reviewed
• [Journal Article] Coupling of an N-Heterocyclic Carbene on Iron with Alkynes Forming η5-Cyclopentadienyl-Diìmine Ligands. (2014)
  • Author(s): T. Hatanaka, Y. Ohki, K. Tatsumi
  • Journal Title: Angew. Chem. Int. Ed Volume: 53 Issue: 10 Pages: 2727-2729
  • DOI: 10.1002/ange.201309021
  • Peer Reviewed
• [Journal Article] Dinuclear Iron (0) Complexes of N-Heterocyclic Carbenes (2014)
  • Author(s): T. Hashimoto, R. Hoshino, T. Hatanaka, Y. Ohki, K. Tatsumi
  • Journal Title: Organometallics Volume: 33 Issue: 4 Pages: 921-929
  • DOI: 10.1021/om401039z
  • Peer Reviewed
• [Journal Article] Snthesis of Coordinatively Unsaturated Half-Sandwich Iron Silyl Complexes Having an N-Heterocyclic Carbene Ligand and Their Reactions with H2. (2013)
  • Author(s): T. Hatanaka, Y. Ohki, K. Tatsumi
  • Journal Title: Eur. J. Inorg. Chem Volume: 33 Issue: 22-23 Pages: 3966-3971
  • DOI: 10.1002/ejic.201300045
  • Peer Reviewed
• [Journal Article] New Synthetic Routes to Metal-Sulfur Clusters Relevant to the Nitrogenase Metallo-Clusters. (2013)
  • Author(s): Y. Ohki, K. Tatsumi
  • Journal Title: Anorg. Allg. Chem Volume: 639 Issue: 8-9 Pages: 1340-1349
  • DOI: 10.1002/zaac.201300081
  • Peer Reviewed
• [Journal Article] Catlytic Generation of Borenium Ions by Cooperative B-H Bond Activation : The Elusive Direct Electrophilic Borylation of Nitrogen Heterocycles with Pinacolborane. (2013)
  • Author(s): T. Stahl, K. e Müther, Y. Ohki, K. Tatsumi, M. Oestreich
  • Journal Title: J. Am. Chem. Soc Volume: 135 Issue: 30 Pages: 10978-10981
  • DOI: 10.1021/ja405925w
  • Peer Reviewed
• [Presentation] Toward Structural and Functional Analogues of the Nitrogenase Active Site (2015)
  • Author(s): Yasuhiro Ohki
  • Organizer: The 95th CSJ Asian International Symposium
  • Place of Presentation: Nihon University
  • Year and Date: 2015-03-27
  • Invited
• [Presentation] ニトロゲナーゼの機能モデル化に向けた第一歩 (2015)
  • Author(s): 大木靖弘
  • Organizer: 分子研研究会
  • Place of Presentation: 岡崎コンファレンスホール
  • Year and Date: 2015-01-06 – 2015-01-07
  • Invited
• [Presentation] ニトロゲナーゼ活性中心の構造と機能の模倣を目指して (2014)
  • Author(s): 大木靖弘
  • Organizer: 第４５回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 中部大学
  • Year and Date: 2014-11-29 – 2014-11-30
  • Invited
• [Presentation] Iron-Sulfur Clusters Structurally Analogous to the FeMo-cofactor of Nitrogenase (2014)
  • Author(s): Yasuhiro Ohki
  • Organizer: Campus Asia Sendai Symposium 2014
  • Place of Presentation: Tohoku University
  • Year and Date: 2014-11-26 – 2014-11-27
  • Invited
• [Presentation] Structural Analogues of Metal-Sulfur Clusters in Reductases: Synthesis and Core Transformations (2014)
  • Author(s): Yasuhiro Ohki
  • Organizer: Vietnam Malaysia International Chemical Congress
  • Place of Presentation: Hanoi (Vietnam)
  • Year and Date: 2014-11-07 – 2014-11-09
  • Invited
• [Presentation] Structural Analogues of Metal-Sulfur Clusters in Reductases: Synthesis and Core Transformations (2014)
  • Author(s): Yasuhiro Ohki
  • Organizer: Malaysian International chemical Congress (18MICC 2014)
  • Place of Presentation: Kuara-Lumpur (Malaysia)
  • Year and Date: 2014-11-03 – 2014-11-05
  • Invited
• [Presentation] N-Heterocyclic Carbene Complexes of Transition Metals Directed Toward Small Molecule Activation and Transformation (2014)
  • Author(s): Yasuhiro Ohki
  • Organizer: Japan-UK Joint Symposium on Coordination Chemistry
  • Place of Presentation: Chuo University
  • Year and Date: 2014-09-17 – 2014-09-19
  • Invited
• [Presentation] Synthesis and Core Transformations of Iron-Sulfur Clusters Modeling the Active Sites of Metallo-Proteins (2014)
  • Author(s): Yasuhiro Ohki
  • Organizer: Inorganic Seminar at the Chemistry Department of Yale University
  • Place of Presentation: Yale University
  • Year and Date: 2014-06-20
  • Invited
• [Presentation] Synthetic Analogues of Metal Centers in Nitrogenase and Iron-Sulfur Enzymes (2014)
  • Author(s): Yasuhiro Ohki
  • Organizer: Gordon Research Conference 2014 on Iron Sulfur Enzymes
  • Place of Presentation: Stonehill College (Easton, MA, USA)
  • Year and Date: 2014-06-15 – 2014-06-20
  • Invited
• [Presentation] Synthesis and Reactions of Coordinatively Unsaturated Iron Complexes of N-Heterocyclic Carbenes (2014)
  • Author(s): Yasuhiro Ohki
  • Organizer: The 17th Joint Symposium of Core-to-Core/IRTG Programs on Elements Function for Transformative Catalysis and Materials
  • Place of Presentation: Nagoya University
  • Year and Date: 2014-06-12 – 2014-06-13
  • Invited
• [Presentation] 酵素活性中心を模倣する鉄-硫黄クラスターの合成と骨格変換 (2014)
  • Author(s): 大木靖弘
  • Organizer: 東京工業大学資源化学研究所講演会
  • Place of Presentation: 東京工業大学資源化学研究所
  • Invited
• [Presentation] 配位不飽和錯体のルテニウム－硫黄部位を反応場とするE-H(E = H, Si, B)結合活性化反応 (2014)
  • Author(s): 大木靖弘
  • Organizer: 新学術領域研究「分子活性化」第６回公開シンポジウム
  • Place of Presentation: 東京工業大学
  • Invited
• [Presentation] Synthesis and Characterization of Iron-Sulfur Cluster Molecules Mimicking the Nitrogenase Metallo-Clusters (2013)
  • Author(s): Yasuhiro Ohki
  • Organizer: Collaborative Conference on 3D and Materials Research 2013
  • Place of Presentation: Jeju, Korea
  • Invited
• [Presentation] 酵素活性中心をなす鉄-硫黄クラスターの自在構築と自在変形への挑戦 (2013)
  • Author(s): 大木靖弘
  • Organizer: 東京工業大学大学院理工学研究科化学専攻講演会
  • Place of Presentation: 東京工業大学
  • Invited
• [Presentation] [NiFe]ヒドロゲナーゼの活性部位モデルとなる有機遷移金属錯体 (2013)
  • Author(s): 大木靖弘
  • Organizer: 第112回触媒討論会
  • Place of Presentation: 秋田大学
  • Invited
• [Presentation] Synthesis of Iron-Sulfur Clusters Mimicking the Nitrogenase Metallo-Clusters (2013)
  • Author(s): Yasuhiro Ohki
  • Organizer: 第63回錯体化学討論会、日韓セッション
  • Place of Presentation: 琉球大学
  • Invited
• [Presentation] N-Heterocyclic Carbene Complexes of Iron for Small Molecule Activation and Transformation (2013)
  • Author(s): Yasuhiro Ohki
  • Organizer: 新学術領域研究「分子活性化」第４回若手シンポジウム
  • Place of Presentation: 鹿児島
  • Invited
• [Remarks]
  • URL: http://inorg.chem.nagoya-u.ac.jp/members/ohki/ohki-j-frame.html