Development of Highly Efficient Metal Complex Catalysis Inspired by Transformations of Small Molecules Promoted by Metalloenzymes

• Project/Area Number: 18065005
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: The University of Tokyo
• Principal Investigator: 溝部 裕司 東大, 生産技術研究所, 教授 (40175609)
• Project Period (FY): 2006 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥32,000,000 (Direct Cost: ¥32,000,000); Fiscal Year 2009: ¥8,000,000 (Direct Cost: ¥8,000,000); Fiscal Year 2008: ¥8,000,000 (Direct Cost: ¥8,000,000); Fiscal Year 2007: ¥8,000,000 (Direct Cost: ¥8,000,000); Fiscal Year 2006: ¥8,000,000 (Direct Cost: ¥8,000,000)
• Keywords: 有機金属化学 / 遷移金属クラスター / 硫黄クラスター / モリブデン錯体 / テトラホスフィン錯体 / 金属錯体触媒 / 金属酵素モデル / 小分子活性化 / 窒素固定 / 金属-スルフィドクラスター / 窒素配位クラスター / DFT計算 / ヒドラジン / 合成化学 / 酵素モデル / 触媒プロセス / 金属スルフィドクラスター / イミド錯体 / 金属テルリドクラスター

Research Abstract

金属酵素活性部位の構造・作用機構に関する最新の情報をもとに、新規な金属錯体触媒を設計・合成し、区活性分子の代表である窒素を初めとする各種小分子を高効率のもとに有用な化合物へと変換する反応系を開拓する。

Research Products

• [Journal Article] Properties and Reactivities of the Hydrido Ligands in the Iridium Sulfido Clusters Relevant to Activation and Production of H2 (2008)
  • Author(s): Hidetake Seino
  • Journal Title: Organometallics 27 Pages: 1275-1289
  • Peer Reviewed
• [Journal Article] Crystal Structure of Ce(IV)/dipicolinate Complex as Catalyst for DNA Hydrolysis (2008)
  • Author(s): H. Katada
  • Journal Title: J. Biol. Inorg. Chem 13 Pages: 249-255
  • Peer Reviewed
• [Journal Article] C-S Bond Cleavage of 2-Methoxythiophene by Ir-TMEDA Complex. Formation of Novel Dinuclear IridathiacyclohexenylComplex (2008)
  • Author(s): Kentaro Iwasa
  • Journal Title: J. Organomet. Chem 693 Pages: 3197-3200
  • Peer Reviewed
• [Journal Article] DFT Study on Chemical N2 Fixation by Using a Cubane-Type RuIr3S4 Cluster. Energy Profile for Binding and Reduction of N2 to Ammonia (2008)
  • Author(s): Hiromasa Tanaka
  • Journal Title: J. Am. Chem. Soc 130 Pages: 9037-9047
  • Peer Reviewed
• [Journal Article] Reactions of Mo(II) Tetraphosphine Complex with a Series of Small Molecules (2008)
  • Author(s): Takeshi Ohnishi
  • Journal Title: J. Organomet. Chem 693 Pages: 269-277
  • Peer Reviewed
• [Journal Article] 金属-硫黄クラスターによる化学的窒素固定 (2008)
  • Author(s): 溝部裕司
  • Journal Title: 学術月報 693 Pages: 3197-3200
• [Journal Article] Isolation of Cubane-Type Metal Sulfido Cluster with a Molecular Nitrogen Ligand (2007)
  • Author(s): H. Mori, H. Seino, M. Hidai, Y. Mizobe
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 5431-5434
• [Journal Article] Isolation of a Cubane-Type Metal Sulfido Cluster with a Molecular NitrogenLigand (2007)
  • Author(s): Hiroyuki Mori
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 5431-5434
  • Peer Reviewed
• [Journal Article] Synthesis of a Sulfido-Capped Trinuclear Cluster and Its Reactions at the Molybdenum Site (2007)
  • Author(s): Hidenobu Kajitani
  • Journal Title: Organometallics 26 Pages: 3499-3508
  • Peer Reviewed
• [Journal Article] Formation of Nitrido and Imido Complexes of Mo and w Containing the Linear Tetraphosphine Ligand (2007)
  • Author(s): Daisuke Watanabe
  • Journal Title: Organometallics 26 Pages: 4909-4920
  • Peer Reviewed
• [Journal Article] Synthesis and X-Ray Structures of Heptanuclear and Decanuclear Mixed-Metal Sulfido Clusters Containing Noble Metals and Group 15 Metals (2007)
  • Author(s): Kazumasa Oya
  • Journal Title: J. Organomet. Chem. 692 Pages: 20-25
• [Journal Article] Synthesis and Characterization of Hydride and Carbonyl RuMo_3S_4 Cubane Clusters (2007)
  • Author(s): Izuru Takei
  • Journal Title: Chem. Lett. 36 Pages: 546-547
• [Journal Article] Addition of Benzenethiol to Terminal Alkynes Catalyzed by Hydrotris-(3,5-dimethylpyrazolyl)borate-Rh(III) Bis(thiolate) Complex : Mechanistic Studies with Characterization of the Key Intermediate (2006)
  • Author(s): Yoshiyuki Misumi
  • Journal Title: J. Organomet. Chem. 691 Pages: 3157-3164
• [Journal Article] Mixed-Metal Sulfido Clusters Containing Noble Metals and Group 15 Metals. Stepwise Construction of Bimetallic and Trimetallic Ru_2MS_2, Ru_2PdSbS_2, and Ru_2Pd_2SbS_2 Cores (2006)
  • Author(s): Takahiko Amitsuka
  • Journal Title: Organometallics 25 Pages: 3034-3039
• [Journal Article] Synthesis of Tellurido-Bridged IrPt_2, IrPd_2,and IrPtPd Clusters by Inserting Zero-Valent Pt and Pd Centers into Te-C bonds (2006)
  • Author(s): Takafumi Nakagawa
  • Journal Title: Angew. Chem. Int. Ed. 45 Pages: 7758-7762
• [Journal Article] Synthesis of Sulfido-, and Thiolato-Bridged Ir3 Cluster an Its Reactions with Alkyne and Isocyanide Including Highly Regioselective Cyclotrimerization of Methyl Propiolte (2006)
  • Author(s): Akihiro Saito
  • Journal Title: J. Organomet. Chem. 691 Pages: 5758-5764
• [Presentation] Reactions of Small Molecules on the Low-Valent Mo Center Surrounded by the Linear Tetraphosphine Ligand (2009)
  • Author(s): Yasushi Mizobe
  • Organizer: International Symposium on Chemistry of Reductases II
  • Place of Presentation: Nagoya, Japan
  • Year and Date: 2009-01-16
• [Presentation] Hydrogen Evolution and H-H Bond Cleavage Promoted by Transition Metal-Sulfido Clusters (2009)
  • Author(s): Y. Mizobe
  • Organizer: Hydrogen & Hydrogen Storage. Methods & Materials
  • Place of Presentation: Bangalore, India
  • Year and Date: 2009-01-05
• [Presentation] Pinacol-Type and McMurry Type Coupling of Aromatic Aldehydes Performed by Tetraphosphine-Molybderium(0) Complex (2008)
  • Author(s): Hidetake Seino
  • Organizer: 2008 Workshop on Organometallic Chemistry
  • Place of Presentation: Beijing, China
  • Year and Date: 2008-10-09
• [Presentation] Isolation of the First Metal-Sulfido Clusters Coordinating Molecular Nitrogen as Functional Model for the Active Site of Nitrogenase (2008)
  • Author(s): Yasushi Mizobe
  • Organizer: 2nd International Symposium on Chemistry of Concerto Catalysis
  • Place of Presentation: Tokyo, Japan
  • Year and Date: 2008-08-18
• [Presentation] Reactions of Ir-Chalcogenolate Complexes with Pt(PPh3)3 : Insertion into Carbon-Chalcogen or Ir=Chalcogen Bond (2008)
  • Author(s): Takafumi Nakagawa
  • Organizer: 23rd International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes, France
  • Year and Date: 2008-07-15
• [Presentation] Addition of Small Molecules to the Bridging Sulfido Ligands in Mixed Transition Metal Clusters (2008)
  • Author(s): Hidetake Seino
  • Organizer: 23rd International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes, France
  • Year and Date: 2008-07-08
• [Presentation] Cubane-Type Sulfido Clusters with N2 Ligand as the New Model of the Active Site of Nitrogenase (2008)
  • Author(s): Yasushi Mizobe
  • Organizer: International Symposium on Chemistry of Reductase
  • Place of Presentation: 名古屋大学
  • Year and Date: 2008-03-11
• [Book] Handbook of Chalcogen Chemistry(分担執筆) (2006)
  • Author(s): Yasushi Mizobe
  • Total Pages: 17
  • Publisher: Royal Society of Chemistry
• [Book] Handbook of Chalcogen Chemistry, Chap. 11.2(F.A. Devillanova, Ed.)
  • Author(s): Y. Mizobe
  • Publisher: Royal Society of Chemistry