Catalysis of Active Site Models of Metalloenzymes Containing Dinuclear Metal Chalcogenide

2009 Fiscal Year Final Research Report

• Project/Area Number: 18065013
• Research Category: Grant-in-Aid for Scientific Research on Priority Areas
• Allocation Type: Single-year Grants
• Review Section: Science and Engineering
• Research Institution: Nagoya University
• Principal Investigator: MATSUMOTO Tsuyoshi Nagoya University, 大学院・理学研究科, 助教 (50311717)
• Project Period (FY): 2006 – 2009
• Keywords: 二核錯体 / カルコゲニド / 金属酵素活性中心 / モデル反応 / 協奏機能触媒

Research Abstract

We have synthesized hetero-dinuclear complexes modeling of the active sites of [NiFe] hydrogenase and acetyl CoA synthase to elucidate the mechanisms of the enzyme functions. The dinuclear Ge/Ru complex bridged by S/OH activates dihydrogen molecule under mild conditions, and their reaction mechanism was investigated. The studies of dinuclear nickel complexes indicates a plausible mechanism of the catalytic pathway of acetyl CoA synthase.

Research Products

• [Journal Article] A Dinuclear Nickel Complex Modeling of the Ni_d(II)-Ni_p(I) State for the Active Site of Acetyl CoA Synthase (2010)
  • Author(s): Matsumoto, T.; Ito, M.; Kotera, M.; Tatsumi, K.
  • Journal Title: Dalton Trans. 39 Pages: 2995-2997
  • Peer Reviewed
• [Journal Article] Host plant genome overcomes the lack of bacterial gene for symbiotic nitrogen fixation (2009)
  • Author(s): Hakoyama, T.; Niimi, K.; Watanabe, H.; Tabata, R.; Matsubara, J.; Sato, S.; Nakamura, Y.; Tabata, S.; Li, J.; Matsumoto, T.; Tatsumi, K.; Nomura, M.; Tajima, S.; Ishizaka, M; Yano, K.; Imaizumi-Anraku, H.; Kawaguchi, M.; Kouchi, H.; Suganuma, N.
  • Journal Title: Nature 462 Pages: 514-517
  • Peer Reviewed
• [Journal Article] Acetyl CoA Synthase, a Key Player of Carbon Fixation in Nature (2009)
  • Author(s): Matsumoto, T.
  • Journal Title: Bull. Jpn. Soc. Coord. Chem. 54(Review) Pages: 38-51
  • Peer Reviewed
• [Journal Article] Evidence for a Rapid Degenerate Hetero-Cope-type Rearrangement in Cp*W(S)_2-CH_2-CH_2-CH=CH_2 (2009)
  • Author(s): Eweiner, F.; Senda, S.; Bergander, K.; Muck-Lichtenfeld, C.; Grimme, S.; Frohlich, R.; Aoyama, M.; Kawaguchi, H.; Ohki, Y.; Matsumoto, T.; Kehr, G.; Tatsumi, K.; Erker, G.
  • Journal Title: Chem. Asian J. 4 Pages: 1830-1833
  • Peer Reviewed
• [Journal Article] Dinuclear Nickel Complexes Modeling the Structure and Function of the Acetyl CoA Synthase Active-Site (2009)
  • Author(s): Ito, M.; Kotera, M.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Proc. Nat. Acad. Sci. USA. 106 Pages: 11862-11866
  • Peer Reviewed
• [Journal Article] Organometallic Chemistry in [NiFe] Hydrogenases: Synthesis of the Structural and Functional Models (2009)
  • Author(s): Matsumoto, T.; Ohki, Y.; Tatsumi, K.
  • Journal Title: J. Syn. Org. Chem. Jpn. 67 Pages: 540-553
  • Peer Reviewed
• [Journal Article] Synthesis and Reactions of Mono- and Dinuclear Nickel(I) Thiolate Complexes (2009)
  • Author(s): Ito, M.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Inorg. Chem. 48 Pages: 2215-2223
  • Peer Reviewed
• [Journal Article] Cationic and Anionic Dinuclear Nickel Complexes [Ni(N_2S_2)Ni(dtc)]^n (n =-1, +1) Modeling the Active Site of Acetyl-CoA Synthase (2009)
  • Author(s): Song, Y.; Ito, M.; Kotera, M.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Chem. Lett. 38 Pages: 184-185
  • Peer Reviewed
• [Journal Article] Structural Models for the Active Site of Acetyl-CoA Synthase: Synthesis of Dinuclear Nickel Complexes having Thiolate, Isocyanide, and Thiourea on the Ni_p Site (2009)
  • Author(s): Ito, M.; Kotera, M.; Song, Y.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Inorg. Chem. 48 Pages: 1250-1256
  • Peer Reviewed
• [Journal Article] Synthesis of Ge_2NiS_4 Clusters and the Thermal Transformation to a Ge_4Ni_6S_<12> Cluster (2008)
  • Author(s): Matsumoto, T.; Matsui, Y., Ito, M.; Tatsumi, K.
  • Journal Title: Inorg. Chem. 47 Pages: 1901-1903
  • Peer Reviewed
• [Journal Article] A Functional Hydrogenase Model: Reversible Interconversion of H_2 and H_2O by a Hydroxo/Sulfido-Bridged Dinuclear Ruthenium-Germanium Complex (2008)
  • Author(s): Matsumoto, T.; Nakaya, Y.; Itakura, N.; Tatsumi, K.
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 2458-2459
  • Peer Reviewed
• [Journal Article] Heterolytic Dihydrogen Activation by a Sulfido- and Oxo-Bridged Dinuclear Germanium-Ruthenium Complex (2008)
  • Author(s): Matsumoto, T.; Nakaya, Y.; Tatsumi, K.
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 1913-1915
  • Peer Reviewed
• [Journal Article] Synthesis of syn-2, 4-Dimercapto-1, 3, 2, 4- dithiadigermetane and Its Application for Ge_2PdS_4 Cluster Synthesis (2008)
  • Author(s): Matsumoto, T.; Matsui, Y.; Ito, M.; Tatsumi, K.
  • Journal Title: Chem. Asian J. 3 Pages: 607-613
  • Peer Reviewed
• [Journal Article] Nickel(II) Thiolate Complexes with a flexible cyclo-{Ni_<10>S_<20>} Framework. (2006)
  • Author(s): Zhang, C.; Takada, S.; Kolzer, M.; Matsumoto, T.; Tatsumi, K.
  • Journal Title: Angew. Chem. Int. Ed. 45 Pages: 3768-3772
  • Peer Reviewed
• [Journal Article] Synthesis of Oxo- and Sulfido-Bridged Germanium-Ruthenium Complexes and Reactions on the Chalcogenido Bridges. (2006)
  • Author(s): Matsumoto, T.; Nakaya, Y.; Tatsumi, K.
  • Journal Title: Organometallics 25 Pages: 4835-4845
  • Peer Reviewed
• [Journal Article] Mono{Hydrotris(mercaptoimidazolyl) borato} Complexes of Manganese(II), Iron(II), Cobalt(II), and Nickel(II) Halides (2006)
  • Author(s): Senda, S.; Ohki, Y.; Hirayama, T.; Toda, D.; Chen, J. -T.; Matsumoto, T.; Kawaguchi, H.; Tatsumi, K.
  • Journal Title: Inorg. Chem. 45 Pages: 9914-9925
  • Peer Reviewed
• [Presentation] Dinuclear Nickel Complexes Modeling the Sructure and Function of Acetyl CoA Synthase (2009)
  • Author(s): Matsumoto, T.
  • Organizer: The 14th International Conference on Bioinorganic Chemistry (ICBIC 14)
  • Place of Presentation: 名古屋
  • Year and Date: 20090725-20090730
• [Presentation] カルコゲン架橋複核錯体を利用した小分子活性化 (2009)
  • Author(s): 松本剛
  • Organizer: 日本化学会第89春季年会特別企画"若手研究者が語る次世代生物無機化学"
  • Place of Presentation: 千葉
  • Year and Date: 20090327-20090330
• [Presentation] Reversible H_2 Activation by Hetero-dinuclear Ru/Ge Complexes: A Functional Hydrogenase Model (2009)
  • Author(s): Matsumoto, T.
  • Organizer: The 1^<st> G-COE International Symposium on Elucidation and Design of Materials and Molecular Functions
  • Place of Presentation: 名古屋
  • Year and Date: 20090113-20090114
• [Presentation] Dihydrogen Activation by Dinuclear Ge-Ru Complexes Modeling [NiFe] Hydrogenase (2008)
  • Author(s): Matsumoto, T.
  • Organizer: The 2^<nd> International Symposium on Concerto Catalysis
  • Place of Presentation: 東京
  • Year and Date: 20080418-20080419
• [Presentation] ヒドロゲナーゼに学ぶゲルマニウムールテニウム複核錯体の可逆な水素活性化 (2007)
  • Author(s): 松本剛
  • Organizer: 東京工業大学理学研究流動機構シンポジウム"元素の個性-どう見るか、どうつくるか、どう使うか-
  • Place of Presentation: 東京
  • Year and Date: 20071129-20071130
• [Presentation] Dinuclear Nickel Complexes modeling Acetyl-CoA Synthase (2007)
  • Author(s): Matsumoto, T.
  • Organizer: The 13th International Conference on Bioinorganic Chemistry (ICBIC 13)
  • Place of Presentation: ウイーン、オーストリア
  • Year and Date: 20070715-20070720
• [Presentation] Dihydrogen Activation by Chalcogenide-bridged Bimetallic Ru-Ge Complexes (2007)
  • Author(s): Matsumoto, T.
  • Organizer: 第1回アジア国際シンポジウム
  • Place of Presentation: 大阪
  • Year and Date: 2007-03-27
• [Presentation] H_2の活性化 (2006)
  • Author(s): 松本剛
  • Organizer: 第56回錯体化学討論会シンポジウム"小分子の活性化新展開"
  • Place of Presentation: 広島
  • Year and Date: 20060916-20060918
• [Presentation] Enzymatic Reaction Models of [NiFe] Hydrogenase and Acetyl-CoA Synthase (2006)
  • Author(s): Matsumoto, T.
  • Organizer: International COE Symposium for Young Scientists on Frontiers of Molecular Science
  • Place of Presentation: 東京
  • Year and Date: 20060825-20060826
• [Remarks] Dalton Trans 2010, 12号の中表紙
• [Remarks] Angew. Chem. Int. Ed. 2006, 23号の口絵(Frontispiece)