Establishment of Spin Controlled Catalysis

• Project/Area Number: 18750155
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Chemistry related to living body
• Research Institution: Toho University
• Principal Investigator: IKEZAKI Akira Toho University, 医学部, 講師 (80297639)
• Project Period (FY): 2006 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥3,840,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥240,000); Fiscal Year 2008: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2007: ¥1,000,000 (Direct Cost: ¥1,000,000); Fiscal Year 2006: ¥1,800,000 (Direct Cost: ¥1,800,000)
• Keywords: 生物無機化学 / 高原子価 / スピン制御 / ポルフィリン金属錯体 / 反強磁陸相互作用 / 反磁性 / 電子配置 / 反強磁性相互作用 / イミダゾール

Research Abstract

高原子価状態の低スピンポルフィリン鉄(III)ラジカルカチオン錯体の電子配置の逆転に成功し、その錯体がS=0の基底状態を有し反磁性的性質があることを明らかにした。1電子酸化体の低スピン状態は従来、1)S=1の鉄(IV)種と2)S=1のポルフィリン鉄(III)ラジカルカチオン錯体が知られているが、今回の研究で第3の型に3)S=0のポルフィリン鉄(III)ラジカルカチオン錯体が示された。

Research Products

• [Journal Article] Models for Cytochromes c' : Observation of an Extremely Labile Spin State in Mono(Imidazole) Complexes of Saddle Shaped Iron(III) Porphyrinates (2009)
  • Author(s): A. Ikezaki, M. Takahashi, and M. Nakamura
  • Journal Title: Angew. Chem. Int. Ed (accepted)
  • Peer Reviewed
• [Journal Article] NMR studies on the electronic structure of one-electron oxidized complexes of iron(III) porphyrinates (2009)
  • Author(s): A. Ikezaki, Y. Ohgo, and M. Nakamura
  • Journal Title: Coord. Chem. Rev (in press)
  • Peer Reviewed
• [Journal Article] NMR Studies on the electronic structure of one- electron oxidized complexes of iron (III) porphyrinates (2009)
  • Author(s): A. Ikezaki, Y. Ohgo, and M. Nakamura
  • Journal Title: Coord. Chem. Rev. (in press)
  • Peer Reviewed
• [Journal Article] Control of electronic structure of a six- coordinate iron (III) porphyrin radical by means of axial ligands (2009)
  • Author(s): A. Ikezaki, H. Tukada, and M. Nakamura
  • Journal Title: Chem. Commun. Pages: 2257-2259
  • Peer Reviewed
• [Journal Article] Control of electronic structure of a six-coordinate iron(III) porphyrin radical by means of axial ligands (2008)
  • Author(s): A. Ikezaki, H. Tukada, and M. Nakamura
  • Journal Title: Chem. Commun Pages: 2257-2259
  • Peer Reviewed
• [Journal Article] Factors that stabilize the (dxz, dyz)3(dxy)1(dz2)1 electron configuration in iron(III) porphyrinates; A case of bis(benzaldehyde) complex (2008)
  • Author(s): A. Ikezaki, Y. Ohgo, T. Watanabe, and M. Nakamura
  • Journal Title: Inorg. Chem. Commun 11 Pages: 1198-1201
  • Peer Reviewed
• [Journal Article] Eletronic Structure of Six-Coordinate Iron(III) Monoazaporphyrin (2008)
  • Author(s): K. Nakamura, A. Ikezaki, Y. Ohgo, T. Ikeue, S. Neya, and M. Nakamura
  • Journal Title: Inorg. Chem 47 Pages: 10299-10307
  • Peer Reviewed
• [Journal Article] Bis-(1-methylimidazole) Complex of Iron(III) Oxypyriporphyrin Adopting an Intermediate-Spin State (2008)
  • Author(s): H. Eguchi, Y. Ohgo, A. Ikezaki, S. Neya, and M. Nakamura
  • Journal Title: Chem. Lett 37 Pages: 768-769
  • NAID: 10021082590
  • Peer Reviewed
• [Journal Article] Electronic ground states of low-spin iron(III) porphyrinoids (2008)
  • Author(s): M. Nakamura, Y. Ohgo, and A. Ikezaki
  • Journal Title: J. Inorg. Biochem 102 Pages: 433-445
  • Peer Reviewed
• [Journal Article] Electronic Properties in a Five-Coordinate Azide Complex of Nonplanar Iron(III) Porphyrin: Revisiting to Quantum Mechanical Spin Admixing (2008)
  • Author(s): S. Neya, A. Takahashi, H. Ode, T. Hsohino, A. Ikezaki, Y. Ohgo, M. Takahashi, V.A. L.-Fonfria, H. Kandori, H. Hiramatsu, T. Kitagawa, J. Teraoka, N. Funasaki, and M. Nakamura
  • Journal Title: Bull. Chem. Soc. Jpn 81 Pages: 136-141
  • Peer Reviewed
• [Journal Article] Factors that stabilize the (dxz, dyz) 3 (dxy) 1 (dz2) 1 electron configuration in iron (III) porphyrinates : A case of bis (benzaldehyde) complex (2008)
  • Author(s): A. Ikezaki, Y. Ohgo, T. Watanabe, and M. Nakamura
  • Journal Title: Inorg. Chem. Commun. 11 Pages: 1198-1201
  • Peer Reviewed
• [Journal Article] Electronic Structure of Six- Coordinate Iron (III) Monoazaporphyrin (2008)
  • Author(s): K. Nakamura, A. Ikezaki, Y. Ohgo, T. Ikeue, S. Neya, and M. Nakamura
  • Journal Title: Inorg. Chem. 47 Pages: 10299-10307
  • Peer Reviewed
• [Journal Article] Bis- (1- methylimidazole) Complex of Iron (III) Oxypyriporphyrin Adopting an Intermediate- Spin State (2008)
  • Author(s): H. Eguchi, Y. Ohgo, A. Ikezaki, S. Neva, and M. Nakamura
  • Journal Title: Chem. Lett. 37 Pages: 768-769
  • NAID: 10021082590
  • Peer Reviewed
• [Journal Article] Electronic ground states of low- spin iron (III) porphyrinoids (2008)
  • Author(s): M. Nakamura, Y. Ohgo, and A. Ikezaki
  • Journal Title: Chem. Commun. Pages: 2257-2259
  • Peer Reviewed
• [Journal Article] Electronic ground states of low-spin iron(III)porphyrinoids (2008)
  • Author(s): M. Nakamura, Y. Ohgo, and A. Ikezaki
  • Journal Title: J. Inorg. Biochem. 102 Pages: 433-445
  • Peer Reviewed
• [Journal Article] Electronic Properties in a Five-Coordinate Azido Complex of Nonplanar Iron (III) Porphyrin: Revisiting to Quantum Mechanical Spin Admixing (2008)
  • Author(s): S. Neya, A. Takahashi, H. Ode, T. Hoshino, A. Ikezaki, Y. Ohgo, M. Takahashi, Y. Furutani, V.A. Lorenz-Fonfria, H. Kandori, H. Hiramatsu, T. Kitagawa, J. Teraoka, N. Funasaki, and M. Nakamura
  • Journal Title: Bull. Chem. Soc. Jpn. 81 Pages: 136-141
  • NAID: 10020139687
  • Peer Reviewed
• [Journal Article] Metal-Porphyrin Orbital Interactions in Highly Saddled Low-Spin Iron(III) Porphyrin Complexes (2007)
  • Author(s): Y. Ohgo, A. Hoshino, T. Okamura, H. Uekusa, D. Hashizume, A. Ikezaki, M. Nakamura
  • Journal Title: Inorg. Chem 46 Pages: 8193-8207
  • Peer Reviewed
• [Journal Article] Magnetic and Infrared Properties of the Azide Complex of (2,7,12,17-Tetrapropylporphycenato)iron(III) : A Novel Admixing Mechanism of the S = 5/2 and S = 3/2 States (2007)
  • Author(s): S. Neya, A. Takahashi, H. Ode, T. Hoshino, M. Hata, A. Ikezaki, Y. Ohgo, M. Takahashi, H. Hiramatsu, T. Kitagawa, Y. Furutani, H. Kandori, N. Funasaki, and M. Nakamura
  • Journal Title: Eur. J. Inorg. Chem 2007 Pages: 3188-3194
  • Peer Reviewed
• [Journal Article] Metal-Porphyrin Orbital Interactions in Highly Saddled Low-Spin Iron(III)Porphyrin Complexes (2007)
  • Author(s): Y. Ohgo, A. Hoshino, T. Okamura, H. Uekusa, D. Hashizume, A. Ikezaki, and M. Nakamura
  • Journal Title: Inorg. Chem. 46 Pages: 8193-8207
  • Peer Reviewed
• [Journal Article] Magnetic and Infrared Properties of the Azide Complex of (2,7,12,17-Tetrapropylporphycenato)iron(III): A Novel Admixing Mechanism of the S=5/2 and S=3/2 States (2007)
  • Author(s): S. Neya, A. Takahashi, H. Ode, T. Hoshino, M. Hata, A. Ikezaki, Y. Ohgo, M. Takahashi, H. Hiramatsu, T. Kitagawa, Y. Furutani, H. Kandori, N. Funasaki, and M. Nakamura
  • Journal Title: Eur. J. Inorg. Chem. 20 Pages: 3188-3194
  • Peer Reviewed
• [Journal Article] 13C NMR Studies of the Electronic Structure of Low-Spin Iron(III) Tetraphenylchlorin Complexes (2006)
  • Author(s): A. Ikezaki, M. Nakamura, S. Juillard, and G. Simonneaux
  • Journal Title: Inorg. Chem 45 Pages: 6728-6739
  • Peer Reviewed
• [Journal Article] 新規なスピンクロスオーバー現象を示す鉄(III)ポルフィリン錯体 (2006)
  • Author(s): 中村幹夫、大胡惠樹、池崎章
  • Journal Title: 機能材料 26 Pages: 38-43
• [Journal Article] ^<13>C NMR Studies of the Electronic Structure of Low-Spin Iron(III) Tetranhenvlchlorin Complexes (2006)
  • Author(s): A.Ikezaki, M.Nakamura, S.Juillard, G.Simonneaux
  • Journal Title: Inorganic Chemistry 45・17 Pages: 6728-6739
• [Presentation] ヘムタンパク質の電子構造を解明するためのメソ13Cプローブ : ミオグロビンケース (2009)
  • Author(s): 池崎章、根矢三郎、鈴木優章、星野忠次・中村幹夫
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
  • Year and Date: 2009-03-30
• [Presentation] ヘムタンパク質の電子構造を解明するためのメソ13Cプローブ:ミオグロビンケース (2009)
  • Author(s): 池崎章、根矢三郎、鈴木優章、星野忠次、中村幹夫
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 船橋
• [Presentation] 異常な電子配置を有する中間スピンヘムの実在 (2009)
  • Author(s): 池崎章、中村真樹
  • Organizer: 第133回東邦医学会例会
  • Place of Presentation: 東京
• [Presentation] Novel Electronic Structure of Six- coordinate Iron (III) Porphyrin Radical (2008)
  • Author(s): A. Ikezaki, H. Tukada, and M. Nakamura
  • Organizer: ASBIC IV (The 4th Asian Biological Inorganic Chemistry Conference)
  • Place of Presentation: Jeju, 韓国
  • Year and Date: 2008-11-13
• [Presentation] Formation and Characterization of the Intermediate-spin Complex with the (d_<xz>, d_<yz>)^3(d_<xy>)^1(d_<z2>)^1 Ground State (2008)
  • Author(s): A. Ikezaki, Y. Ohgo, and M. Nakamura
  • Organizer: ASBIC IV (The 4th Asian Biological Inorganic Chemistry Conference)
  • Place of Presentation: Jeju, 韓国
  • Year and Date: 2008-11-11
• [Presentation] モノ(イミダゾール)ポルフィリン鉄(III)錯体 : シトクロームc'のモデル研究 (2008)
  • Author(s): 池崎章、中村幹夫
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
  • Year and Date: 2008-09-20
• [Presentation] Control of Electronic Structure of Six- Coordinate Iron (III) Porphyrin Radical by Means of Axial Ligands (2008)
  • Author(s): A. Ikezaki, H. Tukada, and M. Nakamura
  • Organizer: ICPP- 5 (Fifth International Conference on Porphyrins and Phthalocyanines)
  • Place of Presentation: Moscow、ロシア
  • Year and Date: 2008-07-10
• [Presentation] Model for Cytochromes c (2008)
  • Author(s): A. Ikezaki and M. Nakamura
  • Organizer: ICPP- 5 (Fifth International Conference on Porphyrins and Phthalocyanines)
  • Place of Presentation: Moscow、ロシア
  • Year and Date: 2008-07-08
• [Presentation] 非平面モノイミダゾールポルフィリン鉄(III)錯体における軸配位子の固定化:シトクロームc'のモデル研究 (2008)
  • Author(s): 池崎 章、 中村 幹夫
  • Organizer: 日本化学会第88春季年会
  • Place of Presentation: 東京
  • Year and Date: 2008-03-28
• [Presentation] Novel Electronic Structure of Six-coordinate Iron(III) Porphyrin Radical (2008)
  • Author(s): A. Ikezaki, H. Tukada, and M. Nakamura
  • Organizer: The 4th Asian Biological Inorganic Chemistry Conference(ASBIC IV)
  • Place of Presentation: Jeju, Korea
• [Presentation] Formation and Characterization of the Intermediate-spin Complex with the (dxz, dyz)3(dxy)1(dz2)1 Ground State (2008)
  • Author(s): A. Ikezaki, Y. Ohgo, and M. Nakamura
  • Organizer: The 4th Asian Biological Inorganic Chemistry Conference(ASBIC IV)
  • Place of Presentation: Jeju, Korea
• [Presentation] モノイミダゾール鉄(III)ポルフィリン錯体における三つのスピン状態間の新規な相互変換 (2008)
  • Author(s): 池崎章、高橋正、中村幹夫
  • Organizer: 第2回東邦大学複合物性研究センターシンポジウム
  • Place of Presentation: 船橋
• [Presentation] 中間スピンを示すサドル型ポルフィリン鉄錯体における軌道間相互作用 (2008)
  • Author(s): 河野壮平、星野哲人、池崎章、大胡惠樹、中村幹夫
  • Organizer: 第2回東邦大学複合物性研究センターシンポジウム
  • Place of Presentation: 船橋
• [Presentation] モノ(イミダゾール)ポルフィリン鉄(III)錯体:シトクロームc'のモデル研究 (2008)
  • Author(s): 池崎章、中村幹夫
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
• [Presentation] ポルフィリン類縁体鉄(III)錯体のスピンクロスオーバー及び電子配置変換挙動 (2008)
  • Author(s): 大胡惠樹、江口創、中村賢一郎、池崎章、根矢三郎、高橋正、橋爪大輔、中村幹夫
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
• [Presentation] 炭素13で特異標識したポルフィリンの合成とヘムタンパク質NMRへの応用 (2008)
  • Author(s): 根矢三郎、鈴木優章、星野忠次、池崎章、中村幹夫
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
• [Presentation] サドル型ポルフィリン鉄錯体における鉄-ポルフィリン軌道間相互作用 (2008)
  • Author(s): 河野壮平、星野哲人、池崎章、大胡惠樹、中村幹夫
  • Organizer: 第58回錯体化学討論会
  • Place of Presentation: 金沢
• [Presentation] Control of Electronic Structure of Six-Coordinate Iron(III) Porphyrin Radical by Means of Axial Ligands (2008)
  • Author(s): A. Ikezaki, H. Tukada, and M. Nakamura
  • Organizer: Fifth International Conference on Porphyrins and Phthalocyanines(ICPP-5)
  • Place of Presentation: Moscow, Russia
• [Presentation] Model for Cytochromes c' (2008)
  • Author(s): A. Ikezaki and M. Nakamura
  • Organizer: Fifth International Conference on Porphyrins and Phthalocyanines(ICPP-5)
  • Place of Presentation: Moscow, Russia
• [Presentation] Unusual electronic structure in iron(III) porphyrinates and their oxidized products (2008)
  • Author(s): M. Nakamura, Y. Ohgo, and A. Ikezaki
  • Organizer: 38th International Conference on Coordination Chemistry
  • Place of Presentation: Jerusalem, Israel
• [Presentation] 非平面モノイミダゾールポルフィリン鉄(III)錯体における軸配位子の固定化、シトクロームc'のモデル研究 (2008)
  • Author(s): 池崎章、中村幹夫
  • Organizer: 第88回日本化学会春季年会
  • Place of Presentation: 東京
• [Presentation] 6配位-モノアザポルフィリン鉄(III)錯体の電子構造 (2008)
  • Author(s): 中村賢一郎、池崎章、大胡惠樹、根矢三郎、中村幹夫
  • Organizer: 第88回日本化学会春季年会
  • Place of Presentation: 東京
• [Presentation] Regulation of heme electronic structure by means of axial ligands and core modification (2008)
  • Author(s): M. Nakamura, Y. Ohgo, and A. Ikezaki
  • Organizer: 1st Zing Conference on Coordination Chemistry
  • Place of Presentation: Cancun, Mexico
• [Presentation] 低スピンポルフィリン鉄(III)錯体の一電子酸化生成物における異常な電子状態 (2007)
  • Author(s): 池崎 章、 中村 幹夫
  • Organizer: 第57回錯体化学討論会
  • Place of Presentation: 名古屋
  • Year and Date: 2007-09-25
• [Presentation] ポルフィリン鉄錯体、ヘムタンパク質から機能材料まで (2007)
  • Author(s): 中村幹夫、大胡惠樹、池崎章、高橋正
  • Organizer: 第4回東邦大学三学部合同学術集会
  • Place of Presentation: 船橋
• [Presentation] 異常な電子状態を示す低スピン-ポルフィリン鉄(III)錯体の一電子酸化生成物 (2007)
  • Author(s): 池崎章、中村幹夫
  • Organizer: 第1回東邦大学複合物性研究センターシンポジウム
  • Place of Presentation: 船橋
• [Presentation] 低スピン-ポルフィリン鉄(III)錯体の一電子酸化生成物における異常な電子状態 (2007)
  • Author(s): 池崎章、中村幹夫
  • Organizer: 第57回錯体化学討論会
  • Place of Presentation: 名古屋
• [Presentation] 6配位オキシピリポルフィリン鉄(III)錯体の電子状態 (2007)
  • Author(s): 江口創、大胡惠樹、池崎章、根矢三郎、中村幹夫
  • Organizer: 第57回錯体化学討論会
  • Place of Presentation: 名古屋
• [Presentation] 2,7,12,17-テトラプロピルポルフィセン鉄(III)錯体に結合したアジドの温度依存的な赤外吸収変化の解析によるスピン状態の考察 (2007)
  • Author(s): 古谷祐詞、根矢三郎、池崎章、大胡惠樹、中村幹夫、神取秀樹
  • Organizer: 第57回錯体化学討論会
  • Place of Presentation: 名古屋
• [Presentation] Formation of iron(III) porphyrinoids with unusual electronic and magnetic properties (2007)
  • Author(s): M. Nakamura, H. Eguchi, Y. Ohgo, A. Ikezaki, and S. Neya
  • Organizer: 13th International Conference on Bioinorganic Chemisrty
  • Place of Presentation: Vienna, Austria
• [Presentation] Unusual electronic and magnetic properties in iron(III) porphyrinoid (2007)
  • Author(s): M. Nakamura, Y. Ohgo, A. Ikezaki, H. Eguchi, and S. Neya
  • Organizer: 1st Georgian Bay International Conference on Bioinorganic Chemistry
  • Place of Presentation: Parry Sound, Canada
• [Presentation] サドル変形モノ-2-メチルベンズイミダゾールポルフィリン鉄(III)錯体の電子構造及び分子構造学的研究:シトクロームc'のモデル研究 (2007)
  • Author(s): 池崎章、中村幹夫
  • Organizer: 第87回日本化学会春期年会
  • Place of Presentation: 大阪
• [Presentation] 低スピン-クロリン鉄(III)錯体の電子状態-ポルフィリン錯体との比較 (2007)
  • Author(s): 小野順平、池崎章、中村幹夫
  • Organizer: 第87回日本化学会春期年会
  • Place of Presentation: 大阪
• [Presentation] オキシピリポルフィリン鉄(III)錯体の電子状態 (2007)
  • Author(s): 江口創、根矢三郎、池崎章、大胡惠樹、中村幹夫
  • Organizer: 第87回日本化学会春期年会
  • Place of Presentation: 大阪
• [Presentation] 低スピンクロリン鉄(III)錯体の電子状態 (2006)
  • Author(s): 池崎章、中村幹夫、G. Simonneaux
  • Organizer: 第56回錯体化学討論会
  • Place of Presentation: 広島
• [Presentation] 酸化型ヘム鉄での中間スピン、高スピン混合系は熱スピン平衡系である (2006)
  • Author(s): 根矢三郎、高橋昭博、畑晶之、星野忠次、池崎章、大胡惠樹、中村幹夫
  • Organizer: 第56回錯体化学討論会
  • Place of Presentation: 広島
• [Presentation] Correlation between the molecular structure and electronic structure in deformed porphyrin manganese complexes (2006)
  • Author(s): A. Ikezaki and M. Nakamura
  • Organizer: 4th International Conference on Porphyrins and Phthalocyanines(ICPP-4)
  • Place of Presentation: Rome, Italy
• [Presentation] ヘムタンパク質の機能を解明するためのモデル研究 (2006)
  • Author(s): 池崎章、大胡惠樹
  • Organizer: 第128回東邦大学医学会例会
  • Place of Presentation: 東京