鉄と銅を基軸とした酸素活性化触媒の理論研究

2016 Fiscal Year Research-status Report

• Project/Area Number: 16K05725
• Research Institution: Kyushu University
• Principal Investigator: 塩田 淑仁 九州大学, 先導物質化学研究所, 准教授 (70335991)
• Project Period (FY): 2016-04-01 – 2020-03-31
• Keywords: 量子化学 / 遷移状態 / メタン活性化 / 電子状態

Outline of Annual Research Achievements

酸化反応の触媒プロセスは、反応活性種の生成とそれに続く基質の挿入によって、開始する。生成する活性種はそれ自身が活性であるために適度に不安定であり、また、活性種が生成されるためには不安定過ぎてもいけない。これらを達成してはじめて触媒がサイクルとして成立する。本研究では理論化学的手法を用いて、“活性中心に鉄と銅を持ち、かつ、酸素分子が酸化剤として働く”反応の触媒サイクル成立要件を解明し、現実の酵素（動作条件は常温常圧）と触媒（動作条件は１００から３００℃、常圧から数気圧）に展開していくことを目的とする。これらを明らかにするために“鉄と銅を基軸とした酸素活性化触媒の理論研究”を行なう。
理論解析の結果から触媒反応における遷移金属の電子状態と反応機構の関係をより深く理解することができた。また実験研究との共同研究を通じて、新しい金属錯体の特異な性質を明らかにするとともに、新しい提案を行なうことができた。その結果は研究成果は国内外の学会での発表や専門誌での掲載などにより公開した。
今後は　さらなら研究を押し進めるため、挑戦的な課題も視野にいれて展開する。

Current Status of Research Progress

1: Research has progressed more than it was originally planned.

Reason

触媒反応における遷移金属の電子状態と反応機構の関係をより深く理解することができた。また実験研究との共同研究を通じて、新しい金属錯体の特異な性質を明らかにするとともに、新しい提案を行なうことができた。その結果は研究成果は国内外の学会での発表や専門誌での掲載などにより公開した。

Strategy for Future Research Activity

当初の予定より　大幅に進捗に進んでいるので　現状維持し
今後は　さらなる研究の展開をはかる。

Research Products

• [Journal Article] An Azulene-Fused Tetracene Diimide with a Small HOMO-LUMO Gap (2017)
  • Author(s): Koide Taro、Takesue Moritaka、Murafuji Toshihiro、Satomi Koichiro、Suzuki Yasutaka、Kawamata Jun、Terai Kengo、Suzuki Mitsuharu、Yamada Hiroko、Shiota Yoshihito、Yoshizawa Kazunari、Tani Fumito
  • Journal Title: ChemPlusChem Volume: 82 Pages: 1010～1014
  • DOI: 10.1002/cplu.201600356
  • Peer Reviewed
• [Journal Article] Anisotropic Change in Magnetic Susceptibility of a Dynamic Single Crystal of Cobalt(II) Complex (2017)
  • Author(s): Yao, Z.-S.; Wu, .S.-Q.;Kitagawa, Y.; Su, S.-Q.; Huang, Y.-G.; Li, G.-L.; Ni, Z.-H.; Nojiri, H.; Shiota, Y.; Yoshizawa, K.; Kang, S.; Kanegawa, S.; Sato, O.
  • Journal Title: Angew Chem. Int. Ed Volume: 56 Pages: 717-721
  • DOI: 10.1002/anie.201606165
  • Peer Reviewed
• [Journal Article] Acid-Base Properties of a Freebase Form of a Quadruply-Ring-Fused Porphyrin Stepwise Protonation Induced by Rigid Ring-Fused Structure (2017)
  • Author(s): Saegusa, Y.; Ishizuka, T.; Shiota, Y.; Yoshizawa, K.; Kojima, T.
  • Journal Title: J. Org. Chem. Volume: 82 Pages: 322-330
  • DOI: 10.1021/acs.joc.6b02419
  • Peer Reviewed
• [Journal Article] Heterometallic FeIII/K coordination polymer with a wide thermal hysteretic spin transition around room temperature (2016)
  • Author(s): Kang, S.; Shiota, Y.; Kariyazaki, A.; Kanegawa, S.; Yoshizawa, K.; Sato, O.
  • Journal Title: Chem. Eur. J. Volume: 22 Pages: 532-538
  • DOI: 10.1002/chem.201503392
  • Peer Reviewed
• [Journal Article] Homogeneous Photocatalytic Water Oxidation with a Dinuclear CoIII-Pyridylmethylamine Complex (2016)
  • Author(s): Ishizuka, T.; Watanabe, A.; Kotani, H.; Hong, D.; Satonaka, K.; Wada, T.; Shiota, Y.; Yoshizawa, K.; Ohara, K.; Yamaguchi, K.; Kato, S.; Fukuzumi, S.; Kojima, T.
  • Journal Title: Inorg. Chem. Volume: 55 Pages: 1154-1164
  • DOI: 10.1021/acs.inorgchem.5b02336
  • Peer Reviewed
• [Journal Article] A new family of anionic FeIII spin crossover complexes featuring a weak-field N2O4 coordination octahedron. (2016)
  • Author(s): Takahashi, K.; Kawamukai, K.; Okai, M.; Mochida, T.; Sakurai, T.; Ohta, H.; Yamamoto, T.; Einaga, Y.; Shiota, Y.; Yoshizawa, K.
  • Journal Title: Chem. Eur. J. Volume: 22 Pages: 1253-1257
  • DOI: 10.1002/chem.201504883
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Synthesis and Structure of a Water-soluble ;-η1:η1-N2 Dinuclear RuII Complex with a Polyamine Ligand (2016)
  • Author(s): Yoshimoto, K.; Yatabe T.; Matsumoto, M.; Robertson, A.; Nakai, H.; Tanaka, H.; Kamachi, K.; Shiota, Y.; Yoshizawa, K.; Asazawa, K. Tanaka, H.; Ogo, S
  • Journal Title: Chem. Lett. Volume: 45 Pages: 149-151
  • DOI: 10.1246/cl.151004
  • Peer Reviewed
• [Journal Article] Possible Peroxo State of the Dicopper Site of Particulate Methane Monooxygenase from Combined Quantum Mechanics and Molecular Mechanics Calculations (2016)
  • Author(s): Itoyama, S.; Doitomi, K.; Kamachi, T.; Shiota, Y.; Yoshizawa, K.
  • Journal Title: Inorg. Chem. Volume: 55 Pages: 2771-2775
  • DOI: 10.1021/acs.inorgchem.5b02603
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Formation and High Reactivity of the anti-Dioxo Form of High-Spin μ-Oxodioxodiiron(IV) as the Active Species That Cleaves Strong C-H Bonds (2016)
  • Author(s): Kodera, M.; Ishiga, S.; Tsuji, T.; Sakurai, K.; Hitomi, Y.; Shiota, Y.; P. K. Sajith; Yoshizawa, K.; Mieda, K.; Ogura, T.
  • Journal Title: Chem. Eur. J. Volume: 22 Pages: 1-14
  • DOI: 10.1002/chem.201600048
  • Peer Reviewed
• [Journal Article] Computational Study of Cyclobutane-1,3-diylidene Dicarbenes: Ground-State Spin Multiplicity and New Strategy Toward the Synthesis of Bicyclo[1.1.0]but-1(3)-enes (2016)
  • Author(s): Fujita, Y.; Abe, M.; Shiota, Y.; Suzuki, T.; Yoshizawa, K.
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 89 Pages: 770-778
  • DOI: 10.1246/bcsj.20160051
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Superior thermoelasticity and shape-memory nanopores in a porous supramolecular organic framework (2016)
  • Author(s): Huang, Y.-G.; Shiota, Y.; Wu, M.-Y.; Su, S.-Q.; Yao, Z.-S.; Kang, S.; Kanegawa, S.; Li, G.-L.; Wu, S.-Q.; Kamachi, T.; Yoshizawa, K.; Ariga, K.; Hong, M.-C.; Sato, O.
  • Journal Title: Nature Commun. Volume: 7 Pages: 11564(1-8)
  • DOI: 10.1038/ncomms11564
  • Peer Reviewed
• [Journal Article] The Role of Coulomb Interactions for Spin Crossover Behaviors and Crystal Structural Transformation in Novel Anionic Fe(III) Complexes from a π-Extended ONO Ligand (2016)
  • Author(s): Murata, S.; Takahashi, K.; Sakurai, T.; Ohta, H.; Yamamoto, T.; Einaga, Y.; Shiota, Y.; Yoshizawa. K.
  • Journal Title: Crystals Volume: 6 Pages: 49(1-16)
  • DOI: 10.3390/cryst6050049
  • Peer Reviewed
• [Journal Article] Mechanistic Insights into C-H Oxidations by Ruthenium(III)-Pterin Complexes: Impact of Basicity of the Pterin Ligand and Electron Ac-ceptability of the Metal Center on the Transition States (2016)
  • Author(s): Mitome, H.; Ishizuka, T.; Kotani, H.; Shiota, Y.; Yoshizawa, K.; Kojima, T.
  • Journal Title: J. Am. Chem. Soc. Volume: 138 Pages: 9508-9520
  • DOI: 10.1021/jacs.6b03785
  • Peer Reviewed
• [Journal Article] Push-Pull Fluorenones and Benzazulenequinones: Regioselective [4 + 2] and [2 + 2] Cycloadditions of Benzopentalenequinone Derivative and Alkynes Bearing an Aniline Moiety (2016)
  • Author(s): Kato, S.-I; Kijima, T.; Shiota, Y.; Yoshihara, T.; Tobita, S.; Yoshizawa, K.; Nakamura, Y.
  • Journal Title: Tetrahedron Lett Volume: 57 Pages: 4604-4607
  • DOI: 10.1016/j.tetlet.2016.09.002
  • Peer Reviewed
• [Journal Article] A Ruthenium(III)-Oxyl Complex Bearing Strong Radical Character (2016)
  • Author(s): Shimoyama, Y.; Ishizuka, T.; Kotani, H.; Shiota, Y.; Yoshizawa, K.; Mieda, K.; Ogura, T.; Okajima, T.; Nozawa, S.; Kojima, T.
  • Journal Title: Angew Chem. Int. Ed. Volume: 55 Pages: 14041-14045
  • DOI: 10.1002/anie.201607861
  • Peer Reviewed
• [Journal Article] Directional Electron Transfer in Crystals of [CrCo] Dinuclear Complexes Achieved by Chirality-assisted Preparative Method (2016)
  • Author(s): Kanegawa, S.; Shiota, Y.; Kang, S.; Takahashi , K.; Okajima, H.; Sakamoto, A.; Iwata, T.; Kandori, H.; Yoshizawa, K.; Sato, O.
  • Journal Title: J. Am. Chem. Soc Volume: 138 Pages: 14170-14173
  • DOI: 10.1021/jacs.6b05089
  • Peer Reviewed
• [Journal Article] Thermally Induced Intra-Carboxyl Proton Shuttle in a Molecular Rack-and-Pinion Cascade Achieving Macroscopic Crystal Deformation (2016)
  • Author(s): Huang, Y.-G.; Shiota, Y. ; Su, S.-Q.; Wu, S.-Q.; Yao, Z.-S.; Li, G.-L.; Kanegawa, S.; Kang, S.; Kamachi, T.; Yoshizawa, K.; Ariga, K.; Sato, O.
  • Journal Title: Angew Chem. Int. Ed. Volume: 55 Pages: 14628-14632
  • DOI: 10.1002/anie.201607886
  • Peer Reviewed
• [Journal Article] Theoretical Study of the Catalytic Hydrogenation of Alkenes by a Disilaferracyclic Complex: Can the Fe-Si σ-Bond-Assisted Activation of H-H Bonds Allow Development of a Catalysis of Iron? (2016)
  • Author(s): Tahara, A.; Tanaka, H.; Sunada, Y.; Shiota, Y.; Yoshizawa, K.; Nagashima, H.
  • Journal Title: J. Org. Chem. Volume: 81 Pages: 10900-10911
  • DOI: 10.1021/acs.joc.6b01961
  • Peer Reviewed / Int'l Joint Research
• [Journal Article] Direct Conversion of Methane to Methanol by Metal-Exchanged ZSM-5 Zeolite (Metal = Fe, Co, Ni, and Cu) (2016)
  • Author(s): Mahyuddin, M.; Staykov, A.; Shiota, Y.; Yoshizawa, K.
  • Journal Title: ACS Catal. Volume: 6 Pages: 8321-8331
  • DOI: 10.1021/acscatal.6b01721
  • Peer Reviewed
• [Presentation] Theoretical Studies of the Catalytic Hydrogenation of Alkenes by a series of Disilametallacyclic iron and ruthenium Complexes (2017)
  • Author(s): TAHARA, Atsushi; TANAKA, Hiromasa; SUNADA, Yusuke; SHIOTA, Yoshihito; YOSHIZAWA, Kazunari; NAGASHIMA, Hideo
  • Organizer: 日本化学会第97春季年会2017
  • Place of Presentation: 慶応大学日吉キャンパス
  • Year and Date: 2017-03-16 – 2017-03-19
• [Presentation] Co-C bond formation reaction via the ligand reduction of cobalt porphycene (2017)
  • Author(s): KOIDE, Taro; SAEKI, Tatsuya; MORITA, Yoshitsugu; SHIOTA, Yoshihito; YOSHIZAWA, Kazunari; SHIMAKOSHI, Hisashi; HISAEDA, Yoshio
  • Organizer: 日本化学会第97春季年会2017
  • Place of Presentation: 慶応大学日吉キャンパス
  • Year and Date: 2017-03-16 – 2017-03-19
• [Presentation] Density Functional Theory calculations of alkane C-H bond activation by iron-oxo complexes bound by nitrogen-containing ligands (2017)
  • Author(s): MATSUI, Misaki; YUMURA, Takashi; WAKASUGI, Takashi; HITOMI, Yutaka; SHIOTA, Yoshihito; YOSHIZAWA, Kazunari
  • Organizer: 日本化学会第97春季年会2017
  • Place of Presentation: 慶応大学日吉キャンパス
  • Year and Date: 2017-03-16 – 2017-03-19
• [Presentation] A Theoretical Study of the Catalytic Hydrogenation of Alkenes by Disilaruthenacyclic Complexes (2017)
  • Author(s): HOSHI, Konoka; TAHARA, Atsushi; SUNADA, Yusuke; TANAKA, Hiromasa; SHIOTA, Yoshihito; YOSHIZAWA, Kazunari; NAGASHIMA, Hideo
  • Organizer: 日本化学会第97春季年会2017
  • Place of Presentation: 慶応大学日吉キャンパス
  • Year and Date: 2017-03-16 – 2017-03-19
• [Presentation] Theoretical study on absorption wavelength control and improvement of light fastness of β-carotene using solid acid. (2017)
  • Author(s): HIROSAWA, Nobuyuki; SHIOTA, Yoshihito; KOHNO, Yoshiumi; ASABA, Ryuma; YOSHIZAWA, Kazunari
  • Organizer: 日本化学会第97春季年会2017
  • Place of Presentation: 慶応大学日吉キャンパス
  • Year and Date: 2017-03-16 – 2017-03-19
• [Presentation] Thermodynamics and photodynamics of a monoprotonated porphyrin directly stabilized by hydrogen bonding (2017)
  • Author(s): SUZUKI, Wataru; KOTANI, Hiroaki; ISHIZUKA, Tomoya; OHKUBO, Kei; SHIOTA, Yoshihito; YOSHIZAWA, Kazunari; FUKUZUMI, Shunichi; KOJIMA, Takahiko
  • Organizer: 日本化学会第97春季年会2017
  • Place of Presentation: 慶応大学日吉キャンパス
  • Year and Date: 2017-03-16 – 2017-03-19
• [Presentation] 膜結合型メタンモノオキシゲナーゼの反応活性種に関する理論的研究 (2016)
  • Author(s): 糸山修平・土井富一城・蒲池高志・塩田淑仁・吉澤一成
  • Organizer: 触媒討論会2016
  • Place of Presentation: 岩手大学
  • Year and Date: 2016-09-21 – 2016-09-23
• [Presentation] 窒素含有鉄オキソ錯体を触媒とするメタンC-H結合活性化に関する速度論的同位体効果 (2016)
  • Author(s): 松井 美咲,湯村 尚史,若杉 隆,人見 穣,塩田 淑仁,吉澤 一成
  • Organizer: 分子科学討論会2016
  • Place of Presentation: 神戸ファッションマート
  • Year and Date: 2016-09-13 – 2016-09-15
• [Presentation] 新奇アニオン性スピンクロスオーバー錯体のπ拡張誘導体の構造と物性 (2016)
  • Author(s): 村田 優,高橋 一志,櫻井 敬博,太田 仁,山本 崇史,栄長 泰明,塩田 淑仁,吉澤 一成
  • Organizer: 分子科学討論会2016
  • Place of Presentation: 神戸ファッションマート
  • Year and Date: 2016-09-13 – 2016-09-15
• [Remarks] 研究業績
  • URL: http://trout.scc.kyushu-u.ac.jp/yoshizawaJ/pagesJ/publicationsJ.html