Controlled Synthesis of Multinuclear Metal Clusters Bridged by Thiolate Ligands

• Project/Area Number: 19550061
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Nagoya University
• Principal Investigator: MATSUMOTO Tsuyoshi Nagoya University, 大学院・理学研究科, 助教 (50311717)
• Project Period (FY): 2007 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2009: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2008: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2007: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000)
• Keywords: 多核金属錯体 / チオラート / スルフィド / ニッケル / 鉄硫黄クラスター / 大環状 / 三座チオラート配位子 / クラスター / 金属クラスター / ニッケル錯体 / ホスト-ゲスト / [4Fe-4S]クラスター / 三座チオラート / ホストーゲスト

Research Abstract

New deca- and dodeca-nuclear cyclic nickel (II) complexes bridged by thioether-thiolate hybrid ligands and tert-butanethiolate ligands have been synthesized, which represents a new addition to the family of large cyclic Ni thiolate cluster. The site-selective nickel-thiolate bonds of the decanuclear complex were cleaved by treatment with I_2 to form a pentanuclear complex assuming a semicircular core structure. We have also synthesized a 3:1 site-differentiated [4Fe-4S] clusters carrying a tridentate thiolate ligand and a carboxylate ligand.

Research Products

• [Journal Article] Dodecanuclear Ellipse and Decanuclear Wheel Nickel(II) Thiolato Clusters with Efficient Femtosecond Nonlinear Absorption (2010)
  • Author(s): Zhang, C. ; Matsumoto, T. ; Samoc, M. ; Petrie, S. ; Meng, S. ; Corkery, T.C. ; Stranger. R. ; Zhang, J. ; Humphrey, M.G. ; Tatsumi. K.
  • Journal Title: Angew. Chem. Int. Ed. (in press)
  • Peer Reviewed
• [Journal Article] A Dinuclear Nickel Complex Modeling of the Nid(II)-Nip(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] Synthesis and Reactions of Mono- and Dinuclear Nickel(I)Thiolate Complexes (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
  • NAID: 120002146280
  • 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
  • NAID: 130000248073
  • Peer Reviewed
• [Journal Article] Evidence for a Rapid Degenerate Hetero-Cope-type Rearrangement in Cp*W(S)2-CH2-CH2-CH=CH2 (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
  • NAID: 10024969046
  • 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(N2S2)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
  • NAID: 130004425442
  • 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 Nip 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] 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
  • NAID: 10024969046
  • Peer Reviewed
• [Journal Article] Dinuclear Nickel Complexes Modeling the Structure and Function of the Acetyl CoA Svnthase 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] 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.; Matsumoto, T.; Kehr, G.; Tatsumi, K.; Erker, G., 他
  • Journal Title: Chem. Asian J. 4 Pages: 1830-1833
  • Peer Reviewed
• [Journal Article] Synthesis and Reactions of Mono- and Dinuclear Nickel(I)Thiolate Complexes (2009)
  • Author(s): Hakoyama, T.; Matsumoto, T.; Tatsumi, K.; Suganuma, N., 他
  • Journal Title: Nature 462 Pages: 514-517
  • Peer Reviewed
• [Journal Article] Structural Models for the Active Site of Acetyl-CoA Synthase : Synthesis of Dinuclear Nicke 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] 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
  • NAID: 10025119498
  • 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] Synthesis of Ge2NiS4 Clusters and the Thermal Transformation to a Ge4Ni6S12 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 H2 and H2O 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 Ge2PdS4 Cluster Synthesis (2008)
  • Author(s): Matsumoto, T. ; Matsui, Y. ; Ito, M. ; Tatsumi, K.
  • Journal Title: Chem. Asian J. 3(Highlighted in the Cover picture) Pages: 607-613
  • Peer Reviewed
• [Journal Article] Modulation of Third-Order Nonlinear Optical Properties by Backbone Modification of Polymeric Pillared-Laver Heterometallic Clusters (2008)
  • Author(s): Zhang, C, Matsumoto, T., Tatsumi, K, 他
  • Journal Title: Adv. Mater. 20 Pages: 1870-1875
  • 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] 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
• [Presentation] 三座チオラート配位子をもつチオラート置換[4Fe-4S]クラスターの酸化還元挙動 (2010)
  • Author(s): 寺田玲季・松本剛・巽和行
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 日(東大阪)
• [Presentation] Synthesis, Reactions and X-ray Structures of Site-Differentiated [4Fe-4S] Clusters (2010)
  • Author(s): 劉東・松本剛・巽和行
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 日(東大阪)
• [Presentation] Ligand Substitution Reactions of the Chloride coordinated [3:1] Site-Differentiated [4Fe-4S] Clusters (2010)
  • Author(s): D. Liu, T. Matsumoto, K. Tatsumi
  • Organizer: The 3rd International Conference on Joint Project of Chemical Synthesis Core Research Institutions
  • Place of Presentation: 名古屋
• [Presentation] Reaction of [4Fe-4S] Clusters Carrying Tridentate Thiolate Ligand TempS3 3- (2010)
  • Author(s): T. Terada, T. Matsumoto, K. Tatsumi
  • Organizer: The 3rd International Conference on Joint Project of Chemical Synthesis Core Research Institutions
  • Place of Presentation: 名古屋
• [Presentation] Reaction of[4Fe-4S]Clusters Carrying Tridentate Thiolate Ligand TempS_3^<3-> (2010)
  • Author(s): T.Terada, T.Matsumoto, K.Tatsumi
  • Organizer: 3rd International Conference on Joint Project of Chemical Synthesis Core Research Institutions
  • Place of Presentation: 名古屋
• [Presentation] Ligand Substitution Reactions of the Chloride-coordinated[3 : 1]Site-Differentiated[4Fe-4S]Clusters (2010)
  • Author(s): D.Liu, T.Matsumoto, K.Tatsumi
  • Organizer: 3rd International Conference on Joint Project of Chemical Synthesis Core Research Institutions
  • Place of Presentation: 名古屋
• [Presentation] Synthesis, Reactions and X-ray Structures of Site-Differentiated[4Fe-4S]Clusters (2010)
  • Author(s): 劉東・松本剛・巽和行
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪
• [Presentation] 三座チオラート配位子をもつチオラート置換[4Fe-4S]クラスターの酸化還元挙動 (2010)
  • Author(s): 寺田玲季・松本剛・巽和行
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 東大阪
• [Presentation] 三座チオラート補助配位子をもつカルボキシラートおよびイミダゾールが配位した[4Fe-4S]クラスターの合成 (2009)
  • Author(s): 寺田玲季・平林聖久・松本剛・巽和行
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 日(長崎)
• [Presentation] Synthesis of [1:3] Site- Differentiated [4Fe-4S] Clusters (2009)
  • Author(s): T. Terada, K. Hirabayashi, T. Matsumoto, K. Tatsumi
  • Organizer: The 14th International Conference on Biological Inorganic Chemistry (ICBIC14)
  • Place of Presentation: 名古屋
• [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
  • Place of Presentation: 日(千葉)
• [Presentation] Synthesis and Reactions of MFe3S4 Clusters (M = Mo, Cu, Ni) Having a Tridentate Ligand Composed of Indolethiolates (2009)
  • Author(s): 劉東・松本剛・巽和行
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
• [Presentation] アコニターゼ活性中心モデルとなる三座チオラート配位子をもつ[4Fe-4S]キュバン型クラスターの合成と反応 (2009)
  • Author(s): 平林聖久・寺田玲季・松本剛・巽和行
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
• [Presentation] 三座チオラート配位子を有する[4Fe-4S]クラスター:[NiFe]ヒドロゲナーゼに存在する[4Fe-4S]distクラスターモデル構築 (2009)
  • Author(s): 寺田玲季・松本剛・巽和行
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
• [Presentation] Synthesis of 1:3 Site-Differentiated [4Fe-4S] Clusters Modeling Aconitase Active Site and [4Fe-4S]dist Cluster of Hydrogenases (2009)
  • Author(s): T. Terada, K. Hirabayashi, T. Matsumoto, K. Tatsumi
  • Organizer: International Symposium on Chemistry of Reductase II
  • Place of Presentation: 名古屋
• [Presentation] Synthesis of[1 : 3]Site-Differentiated[4Fe-4S]Clusters (2009)
  • Author(s): T.Terada, K.Hirabayashi, T.Matsumoto, K.Tatsumi
  • Organizer: 14th International Conference on Biological Inorganic Chemistry(ICBIC14)
  • Place of Presentation: 名古屋
• [Presentation] 三座チオラート補助配位子をもつカルボキシラートおよびイミダソールが配位した[4Fe-4S]クラスターの合成 (2009)
  • Author(s): 寺田玲季・平林聖久・松本剛・巽和行
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎
• [Presentation] 三座チオラート配位子を有する[4Fe-4S]クラスター : [NiFe]ヒドロゲナーゼに存在する[4Fe-4S]_<dist>ラスターモデル構築 (2009)
  • Author(s): 寺田玲季, 松本剛, 巽和行
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
• [Presentation] Synthesis and Reactions of MFe_3S_4 clusters (M=Mo, Cu, Ni) havine a Tridentate Ligand Composed of Indolethiolates (2009)
  • Author(s): 劉東, 松本剛, 巽和行
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
• [Presentation] Synthesis of 1:3 Site-Differentiated [4Fe-4S] Clusters Modeling Aconitase Active Site and [4Fe-4S]_<dist> Cluster of Hydrogenases (2009)
  • Author(s): T. Terada, K. Hirabayashi, T. Matsumoto, K. Tatsumi
  • Organizer: International Symposium on Chemistry of Reductase II
  • Place of Presentation: 名古屋
• [Presentation] Synthesis and Reactions of Dinuclear Fe-Ni Complexes Having Bis(trimethylsilyl)amides on Fe (2008)
  • Author(s): 劉東・松本剛・巽和行
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
• [Presentation] ベンゼン環に3つの3-メルカプト-6-メトキシフェニル基を連結した三座チオラート配位子をもつ[4Fe-4S]クラスター (2008)
  • Author(s): 寺田玲季・松本剛・巽和行
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
• [Presentation] Synthesis and Site Selective Substitution of [4Fe-4S] Clusters Bearing the Tridentate Ligand Composed of Fluorobenzenethiolate (2008)
  • Author(s): T. Wakimoto, T. Matsumoto, K. Tatsumi
  • Organizer: International Symposium on Chemistry of Reductase
  • Place of Presentation: 名古屋
• [Presentation] Synthesis and Reactions of Dinuclear Fe-Ni Complexes Having Bis(trimethylsilyl)amides on Fe. (2008)
  • Author(s): 劉東, 松本剛, 巽和行
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
• [Presentation] Synthesis and Site Selective Substitution of [4Fe-4S] Clusters Bearing the Tridentate Ligand Composed of Fluorobenzenethiolate (2008)
  • Author(s): T. Wakimoto, T. Matsumoto, K. Tatsumi
  • Organizer: International Symposium on Chemistry of Reductases
  • Place of Presentation: 名古屋
• [Presentation] Dinuclear Nickel Complexes modeling Acetyl-CoA Synthase (2007)
  • Author(s): T. Matsumoto
  • Organizer: The 13th International Conference on Bioinorganic Chemistry (ICBIC 13)
  • Place of Presentation: ウイーン、オーストリア
• [Remarks] 成果は論文誌の表紙等に取り上げられた
• [Remarks] Chem Asian J. 2008, 3号の表紙
• [Remarks] Angew. Chem. Int. Ed. 2010 (in press)の中表紙
• [Remarks]
  • URL: http://inorg.chem.nagoya-u.ac.jp
• [Remarks]
  • URL: http://inorg.chem.nagoya-u.ac.jp