Synthesis and Control of Oxidation Reactivity of Metal Complexes Having Active-oxygen Species

2009 Fiscal Year Self-evaluation Report

• Project/Area Number: 19350029
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Kanazawa University
• Principal Investigator: SUZUKI Masatatsu Kanazawa University, 物質化学系, 教授 (20091390)
• Project Period (FY): 2007 – 2009
• Keywords: 生物無機化学 / 合成化学 / 酸素活性種 / 機能モデル / 酸素錯体 / 反応活性種

Research Abstract

生体系にある金属酵素は,活性部位である金属中心と,そのまわりの蛋白質が作りだす反応場との共同効果により,高効率かつ選択的な特異的機能を発現している。特に金属酵素は,酸素分子の代謝に深く関わっており,酸素分子の運搬や酸化反応による物質変換,水への還元によるエネルギー獲得,さらにはその逆反応である水の酸化による酸素発生で重要な役割を果たしている。このような特異機能を有する物質の創製は,合成化学の重要な課題であるが,まだこの様な酵素類似機能を持つ物質群の創製は難しい。
本研究では,金属イオンの基本的性質である酸化還元能および多様な立体化学を分子レベルで制御して非ヘム鉄型金属蛋白質や酵素(本研究ではヘム鉄以外の金属蛋白質や酵素を示している)の機能モデル錯体の創製を目指す。すなわち,反応中間体の機能モデルとなる活性中心と,反応基質の取込みが可能な反応場を構築して,様々な酸化能を有する酸素活性種を自在に創製する。さらにその構造及び電子状態と反応性相関を明らかにして,機能発現機構を分子レベルで解明する。

Research Products

• [Journal Article] Aliphatic C-H Bond Activation Initiated by a (μ-η^2:η^2-Peroxo)dicopper(II) Complex in Comparison with Cumylperoxyl Radical (2009)
  • Author(s): T. Matsumoto, K. Ohkubo, K. Honda, A. Yazawa, H. Furutachi, S. Fujinami, S. Fukuzumi, M. Suzuki
  • Journal Title: J.Am.Chem.Soc. 131 Pages: 9258-9267
  • Peer Reviewed
• [Journal Article] Oxidation Reactivity of a Bis(μ-oxo)-dinickel(III) Complex : Arene Hydroxylation of the Supporting Ligand (2009)
  • Author(s): K. Honda, J. Cho, T. Matsumoto, J. Roh, H. Furutachi, T. Tosha, M. Kubo, S. Fujinami, T. Ogura, T. Kitagawa, M. Suzuki
  • Journal Title: Angew.Chem.Int.Ed. 48 Pages: 3304-3307
  • Peer Reviewed
• [Journal Article] Reactions of Copper(II)-H_2O_2 Adducts Supported by Tridentate Bis(2-pyridylmethyl)-amine Ligands : Sensitivity to Solvent and Variations in Ligand Substitution (2008)
  • Author(s): A. Kunishita, J. D. Scanlon, H. Ishimaru, K. Honda, T. Ogura, M. Suzuki, C. J. Cramer, S. Itoh
  • Journal Title: Inorg.Chem. 47 Pages: 8222-8232
  • Peer Reviewed
• [Journal Article] Ligand Effects on Dioxygen Activation by Copper and Nickel Complexes : Reactivity and Intermediates (2007)
  • Author(s): M. Suzuki
  • Journal Title: Acc.Chem.Res. 40 Pages: 609-617
  • Peer Reviewed
• [Journal Article] Synthesis and Reactivity of (μ-η^2:η^2-Peroxo)dicopper(II) Complexes with Dinucleating Ligands : Hydroxylation of Xylyl Linker with a NIH Shift (2007)
  • Author(s): T. Matsumoto, H. Furutachi, S. Nagatomo, T. Tosha, S. Fujinami, T. Kitagawa, M. Suzuki
  • Journal Title: J.Organometal., Chem. 692 Pages: 111-121
  • Peer Reviewed
• [Presentation] Oxidation Reactivities of Peroxo-diiron(III) and -dicopper(II) Complexes : Functional Models for Dioxygen Activating Dimetallo-enzymes (2009)
  • Author(s): M. Suzuki
  • Organizer: 14th International Conference on Biological Inorganic Chemistry
  • Place of Presentation: Nagoya, Japan
  • Year and Date: 2009-07-27
• [Presentation] Oxidation Reactivities of Peroxo-diiron(III) and -dicopper(II) Complexes : Functional Models for Dioxygen Binding and Activating Diiron and Dicopper Metalloenzymes (2008)
  • Author(s): M. Suzuki
  • Organizer: The 4th Asian Biological Inorganic Chemistry Conference
  • Place of Presentation: Jeju, Korea
  • Year and Date: 2008-11-11
• [Presentation] Reactivity of Peroxodiiron(III), (μ-η^2:η^2-Peroxo)dicopper(II), and Bis(μ-oxo) dinickel(III) Complexes (2008)
  • Author(s): M. Suzuki
  • Organizer: Global COE in Chemistry, Nagoya Special Symposium, Dioxygen Activation by Metalloenzymes and Models
  • Place of Presentation: Nagoya, Nagoya University, Japan
  • Year and Date: 2008-03-21
• [Presentation] Reactivity of Peroxodiiron(III) and Dicopper(II) Complexes : Functional Models for Dioxygen Binding and Activating Diiron and Dicopper Metalloenzymes (2007)
  • Author(s): M. Suzuki
  • Organizer: The 67th Okazaki Conference, Molecular Science and Chemical Biology of Biomolecular Function
  • Place of Presentation: Okazaki, Japan
  • Year and Date: 2007-10-12
• [Presentation] Reversible Dioxygen Binding vs Arene Hydroxylation Mediated by Peroxo-diiron(III) Complexes (2007)
  • Author(s): M. Suzuki
  • Organizer: The First Asian Conference on Coordination Chemistry
  • Place of Presentation: Okazaki, Japan
  • Year and Date: 2007-08-01
• [Book] 化学(二核鉄中心で酸素分子を活性化-ペルオキソ錯体のモデル研究) (2009)
  • Author(s): 古舘秀樹, 鈴木正樹
  • Total Pages: 66-67