Organometallic and Cluster Chemistry in M+I40etalloenzymes with Reducing Activities

2010 Fiscal Year Final Research Report

• Project/Area Number: 18GS0207
• Research Category: Grant-in-Aid for Creative Scientific Research
• Allocation Type: Single-year Grants
• Research Institution: Nagoya University
• Principal Investigator: TATSUMI Kazuyuki 名古屋大学, 物質科学国際研究センター, 教授 (10155096)
• Co-Investigator(Kenkyū-buntansha): KAZUNARI Yoshizawa 九州大学, 先導物質化学研究所, 教授 (30273486) ; HIGUCHI Yoshiki 兵庫県立大学, 大学院・生命理学研究科, 教授 (90183574) ; KAWAGUCHI Hiroyuki 東京工業大学, 大学院・理工学研究科, 教授 (20262850) ; MATSUMOTO Tsuyoshi 名古屋大学, 大学院・理学研究科, 助教 (50311717) ; OHKI Yasuhiro 名古屋大学, 大学院・理学研究科, 准教授 (10324394)
• Project Period (FY): 2006 – 2010
• Keywords: 金属-硫黄クラスター / ニトロゲナーゼ / ヒドロゲナーゼ / 還元系金属酵素

Research Abstract

Through the integration of coordination/organometallic chemistry, structural biology, and theoretical chemistry, we have undertaken the chemical study of reductases, the importance of which has been noticed recently in connection with social needs for energy and food. Our accomplishments in this program have exceeded our expectations, and we have achieved significant results that provide clues in understanding the enzymatic function of reductases at the cluster active sites. We have succeeded in synthesizing favourable models of the active-sites of nitrogenase and hydrogenase, and their physicochemical properties have been clarified, enabling us to study the chemistry of these enzymes. From the theoretical analysis of the newly synthesized dinuclear complex that activates dinitrogen, we revealed its reaction mechanism, which also provides us with important information concerning the reaction mechanisms of nitrogenase and hydrogenases. We have also discovered the novel[4Fe-3S] cluster in the structure of an oxygen-tolerant[NiFe] hydrogenase.

Research Products

• [Journal Article] Synthesis and Reactivity of Niobium Complexes Having a Tripodal Triaryloxide Ligand in Bidentate, Tridentate, and Tetradentate Coordination Modes (2011)
  • Author(s): F. Akagi, Y. Ishida, T. Matsuo, and H. Kawaguchi
  • Journal Title: Dalton Trans. Volume: 40 Pages: 2375-2382
  • DOI: DOI:10.1039/b911082h
  • Peer Reviewed
• [Journal Article] Structural Basis for a[4Fe-3S] Cluster in the Oxygen-tolerant Membrane-bound[Ni-Fe]-hydrogenase (2011)
  • Author(s): Y. Shomura, K. Yoon, H. Nishihara, Y. Higuchi
  • Journal Title: Nature Volume: 479 Pages: 253-257
  • DOI: DOI:10.1038/nature10504
  • Peer Reviewed
• [Journal Article] Molybdenum-Catalyzed Transformation of Molecular Dinitrogen into Silylamine : Experimental and DFT Study on Remarkable Role of Ferrocenyldiphosphine Ligands (2011)
  • Author(s): H. Tanaka, A. Sasada, T. Kouno, M. Yuki, Y. Miyake, H. Nakanishi, Y. Nishibayashi, K. Yoshizawa
  • Journal Title: Am. Chem. Soc. Volume: 133 Pages: 3498-3506
  • DOI: DOI:10.1021/ja109181n
  • Peer Reviewed
• [Journal Article] Computational Evidences for Hydrogen Generation via Reductive Cleavage of Water andα-H Abstraction on a Molybdenum Complex (2011)
  • Author(s): J. Li, K. Yoshizawa
  • Journal Title: Angew. Chem. Int. Ed. Volume: 50 Pages: 11972-11975
  • DOI: DOI:10.1002/anie.201102917
  • Peer Reviewed
• [Journal Article] A Model for the CO-Inhibited Form of[NiFe] Hydrogenase : Synthesis of(CO) 3Fe(μ-StBu) 3Ni{SC6H3-2, 6-(mesityl) 2} and Reversible CO Addition at the Ni Site (2010)
  • Author(s): Y. Ohki, K. Yasumura, M. Ando, S. Shimokata, K. Tatsumi
  • Journal Title: Proc. Natl. Acad. Sci. U. S. A Volume: 107 Pages: 3994-3997
  • DOI: DOI:10.1073/pnas.0913399107
• [Journal Article] Dinuclear Nickel Complexes Modeling the Structure and Function of the Acetyl CoA Synthase Active-Site (2009)
  • Author(s): M. Ito, M. Kotera, T. Matsumoto, K. Tatsumi
  • Journal Title: Proc. Natl. Acad. Sci. U. S. A Volume: 106 Pages: 11862-11866
  • DOI: DOI:10.1073/pnas.0900433106
  • Peer Reviewed
• [Journal Article] Synthesis, Structures, and Electronic Properties of[8Fe-7S] Cluster Complexes Modeling the Nitrogenase P-Cluster (2009)
  • Author(s): Y. Ohki, M. Imada, A. Murata, Y. Sunada, S. Ohta, M. Honda, T. Sasamori, N. Tokitoh, M. Katada, K. Tatsumi
  • Journal Title: J. Am. Chem. Soc. Volume: 131 Pages: 13168-13178
  • DOI: DOI:10.1021/ja9055036
• [Journal Article] Host Plant Genome Overcomes the Lack of a Bacterial Gene for Symbiotic Nitrogen Fixation (2009)
  • Author(s): T. Hakoyama, K. Niimi, H. Watanabe, R. Tabata, J. Matsubara, S. Sato, Y. Nakamura, S. Tabata, J. Li, T. Matsumoto, K. Tatsumi, M. Nomura, S. Tajima, M. Ishizuka, K. Yano, H. Imaizumi-Anraku, M. Kawaguchi, H. Kouchi, N. Suganuma
  • Journal Title: Nature Volume: 462 Pages: 514-518
  • DOI: DOI:10.1038/nature08594
  • Peer Reviewed
• [Journal Article] Reductive Coupling of Six Carbon Monoxides by a Ditantalum Hydride Complex (2009)
  • Author(s): T. Watanabe, Y. Ishida, T. Matsuo, H. Kawaguchi
  • Journal Title: J. Am. Chem. Soc. Volume: 131 Pages: 3474-3475
  • DOI: DOI:10.1021/ja9007276
  • Peer Reviewed
• [Journal Article] [NiFe] hydrogenases : structural and spectroscopic studies of the reaction mechanism (2009)
  • Author(s): H. Ogata, W. Lubitz, Y. Higuchi
  • Journal Title: Dalton Trans. Volume: 37 Pages: 7577-7587
  • DOI: DOI:10.1039/b903840j
  • Peer Reviewed
• [Journal Article] Thiolate-bridged dinuclear iron(tris-carbonyl)-nickel complexes relevant to the active site of[NiFe] hydrogenase (2008)
  • Author(s): Y. Ohki, K. Yasumura, K. Kuge, S. Tanino, M. Ando, Z. Li, K. Tatsumi
  • Journal Title: Proc. Natl. Acad. Sci. U. S. A Volume: 105 Pages: 7652-7657
  • DOI: DOI:10.1073/pnas.0800538105
  • 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 via Ru-N-NHx(x=1-3) Intermediates with Unique Structures (2008)
  • Author(s): H. Tanaka, H. Mori, H. Seino, M. Hidai, Y. Mizobe, K. Yoshizawa
  • Journal Title: J. Am. Chem. Soc. Volume: 130 Pages: 9037-9047
  • DOI: DOI:10.1021/ja8009567
  • Peer Reviewed
• [Journal Article] Quantum Chemical Approach to the Mechanism for the Biological Conversion of Tyrosine to Dopaquinone (2008)
  • Author(s): T. Inoue, Y. Shiota, K. Yoshizawa
  • Journal Title: J. Am. Chem. Soc. Volume: 130 Pages: 16890-16897
  • DOI: DOI:10.1021/ja802618s
  • Peer Reviewed
• [Journal Article] Synthesis of New[8Fe-7S] Clusters : A Topological Link Between the Core Structures of P-cluster, FeMo-co, and FeFe-co of Nitrogenases (2007)
  • Author(s): Y. Ohki, Y. Ikagawa, K. Tatsumi
  • Journal Title: J. Am. Chem. Soc Volume: 129 Pages: 10457-10465
  • DOI: DOI:10.1021/ja072256b
  • Peer Reviewed
• [Journal Article] Dinitrogen Cleavage by a Diniobium Tetrahydride Complex : Formation of a Nitride and Its Conversion to Imide Species (2007)
  • Author(s): F. Akagil, T. Matsuo, H. Kawaguchi
  • Journal Title: Angew. Chem. Int. Ed. Volume: 46 Pages: 8778-8781
  • DOI: DOI:10.1002/anie.200703336
  • Peer Reviewed
• [Journal Article] The DIX domain of Dishevelled confers Wnt signaling by dynamic polymerization (2007)
  • Author(s): T. Schwarz-romond, M. Fiedler, N. Shibata, P. J. G. Butler, A. Kikuchi, Y. Higuchi, M. Beinz
  • Journal Title: Nat. Struct. Mol. Biol Volume: 14 Pages: 484-492
  • DOI: DOI:10.1038/nsmb1247
  • Peer Reviewed
• [Presentation] Small Molecule Activation by Group 5 Metal Hydrides Having Aryloxide Ligands (2011)
  • Author(s): H. Kawaguchi
  • Organizer: 3rd Erlangen Symposium on Redox-Active Metal Complexes : Control of Reactivity via Molecular Architecture
  • Place of Presentation: Erlangen, Germany
  • Year and Date: 20111005-08
• [Presentation] Computational Mutation of Enzymatic Reactions (2011)
  • Author(s): K. Yoshizawa
  • Organizer: International Symposium of Homogeneous and Heterogeneous Catalysis XV
  • Place of Presentation: Berlin Free University, Berlin, Germany
  • Year and Date: 20110911-16
• [Presentation] 酸素耐性膜結合型[NiFe]ヒドロゲナーゼのX線結晶構造解析-水素エネルギー利用に向けた基礎科学的研究- (2011)
  • Author(s): 樋口芳樹
  • Organizer: 関西サイエンスフォーラム
  • Place of Presentation: 大阪
  • Year and Date: 2011-11-29
• [Presentation] 還元系金属酵素の化学-自然に学ぶ- (2011)
  • Author(s): 巽和行
  • Organizer: The 5^<th> Waseda GCOE International Symposium on "Practical Chemical Wisdom"
  • Place of Presentation: 早稲田大学理工
  • Year and Date: 2011-01-13
• [Presentation] 還元系金属酵素の有機金属化学 (2010)
  • Author(s): 巽和行
  • Organizer: 有機合成化学協会講習会
  • Place of Presentation: 東京
  • Year and Date: 2010-06-23
• [Presentation] Activation of H2 by S-donor/O-donor-bridged Heterodunuclear Complexes relevant to the Function of[NiFe] Hydrogenase (2009)
  • Author(s): K. Tatsumi, T. Matsumoto, Y. Ohki
  • Organizer: International Conference on Hydrogen and Hydrogen Storage : Methods and Materials
  • Place of Presentation: Bangalore, India
  • Year and Date: 20090703-06
• [Presentation] フェノキシド多座配位子を用いた多核錯体反応場の構築と反応 (2008)
  • Author(s): 川口博之
  • Organizer: 第58回錯体化学討論会(シンポジウム:ヘテロ元素架橋多核サイトでの特異な反応性)
  • Place of Presentation: 金沢大学
  • Year and Date: 20080920-22
• [Presentation] Metal-Sulfide-Cluster Synthesis? Challenge to Model the Active Sites of Reductases- (2007)
  • Author(s): K. Tatsumi
  • Organizer: The 5th National Symposium on Structural Chemistry(5^<th> NSSC)
  • Place of Presentation: Fuzhou, China
  • Year and Date: 20071025-31
• [Presentation] 古くて新しい還元系金属酵素?生物無機化学の新展開,「金属イオンを含む新しい生体分子の創製と実践的活用」 (2007)
  • Author(s): 巽和行
  • Organizer: 錯体化学討論会、シンポジウム
  • Place of Presentation: 名古屋
  • Year and Date: 2007-09-25
• [Presentation] Active site of[NiFe] hydrogenase-inhibited, unready, ready and active states (2006)
  • Author(s): Y. Higuchi
  • Organizer: 8th European Biological Inorganic Chemistry Conference(EUROBIC8)
  • Place of Presentation: Portugal
  • Year and Date: 20060702-06
• [Presentation] Recent Progress in the Synthesis of Fe/S abd Fe/Mo/S Clusters
  • Author(s): K. Tatsumi
  • Organizer: 24^<th> Latin American Chemistry Congress
  • Place of Presentation: Cartagena, Colombia
  • Year and Date: 00000927-1001
• [Remarks] 受賞等巽和行、平成23年サイボルト賞(ドイツ)
• [Remarks] 巽和行、平成23年ミュンスター大学名誉博士号(ドイツ)
• [Remarks] 大木靖弘、第58回日本化学会進歩賞
• [Remarks] 大木靖弘、平成21年度文部科学大臣表彰若手科学者賞
• [Remarks] 吉澤一成、第28回日本化学会学術賞
• [Remarks] 吉澤一成, BCSJ賞、平成20年10月
• [Remarks]
  • URL: http://inorg.chem.nagoya-u.ac.jp/frame.html
• [Remarks] 報道等(a)雑誌論文(12)の内容が下記に報道される.NHKニュース，毎日新聞，産経新聞，日本経済新聞，神戸新聞，化学工業日報，朝日コム(平成23年10月17日),Chemical & Engineering News(October 24, 2011 Vol.89, No.43, P37), Angewandte Highlights(DOI:10.1002/anie.201108761).
• [Remarks] (b)雑誌論文(1)の内容がScience誌のEditor’s Choiceに紹介される(Science 2007,317,1297).