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2016 Fiscal Year Research-status Report

Oxygenation of methane into methanol with organocobalt complexes under ambient conditions

Research Project

Project/Area Number 16K13964
Research InstitutionOsaka University

Principal Investigator

大久保 敬  大阪大学, 未来戦略機構, 招へい教授 (00379140)

Project Period (FY) 2016-04-01 – 2018-03-31
Keywordsメタン酸化 / 酸化反応 / コバルト / 光反応 / ラジカル / 連鎖反応 / 酸素酸化
Outline of Annual Research Achievements

メタンからメタノールへの酸化反応は最も難しい化学反応の1つである。本研究では、メタンのC-H結合をメチルラジカルの強力な水素引き抜き能を利用することでメタノールへの酸素酸化を達成しようというこれまでにない全く新しいタイプの反応開発をすることを目指した。
実験は次のような手順で行った。まずメチルコバロキシムを、文献記載の方法にて合成した。合成したコバルト錯体をメタンと酸素の混合気体雰囲気下アセトニトリル中で光照射を行った。その結果、微量のメタノールがの生成が確認された。反応機構は次のように想定している。光照射によってコバルト(III)錯体のCo(III)-C結合が開裂する。ここで生成するメチルラジカルは溶媒殻内で元の錯体に戻ろうとするが、メタン濃度が高い条件下では、フリーのメタンから水素を引き抜き、その時点でフリーのメチルラジカルが生成する。このメチルラジカルは分子上酸素を即座に捕捉されることによって、メチルペルオキシルラジカルが生成する。このメチルペルオキシルラジカルは、大過剰に存在するメタンからさらに水素を引き抜き、メタンヒドロペルオキシドを与え、それが分解することによって最終生成物であるメタノールへ至る。ここで水素引き抜きによってさらにもう一分子のメチルラジカルが生成し連鎖的に反応は進む。
本反応を進行させるためには、溶媒の選択が必要不可欠であった。通常メチルラジカルは、有機溶媒のC-H結合を切断し水素を得てメタンを生成、あるいは、エタンへの二量化反応によって不活性化する。そこで、本研究では、溶媒としてフルオラス溶媒を用いた。フルオラス溶媒は、芳香族系と脂肪族系のものが現在市販されているが、メチルラジカルの付加を防ぐために、脂肪族系のフルオラス溶媒を中心に検討を行った結果テトラデカフルオロヘキサン(フロリナートFC72)が最も有効であることを見いだした。

Current Status of Research Progress
Current Status of Research Progress

2: Research has progressed on the whole more than it was originally planned.

Reason

28年度の研究計画として提案したとおり、有機コバロキシムを用いてメタノールが生成物として得られる段階まで達した。

Strategy for Future Research Activity

有機コバロキシムを用いてメタノールが生成物として得られる段階までは当初の計画通りだが、収率がまだ低くメチルコバロキシムの分解によってもメタノールが得られるので、現状その区別は難しい状況であるので今後さらに条件検討を行う予定である。

  • Research Products

    (40 results)

All 2017 2016 Other

All Int'l Joint Research (3 results) Journal Article (26 results) (of which Int'l Joint Research: 26 results,  Peer Reviewed: 26 results,  Acknowledgement Compliant: 25 results,  Open Access: 12 results) Presentation (10 results) (of which Int'l Joint Research: 4 results,  Invited: 3 results) Patent(Industrial Property Rights) (1 results)

  • [Int'l Joint Research] 梨花女子大学(韓国)

    • Country Name
      KOREA (REP. OF KOREA)
    • Counterpart Institution
      梨花女子大学
  • [Int'l Joint Research] ミゲルフェルナンデス大(スペイン)

    • Country Name
      SPAIN
    • Counterpart Institution
      ミゲルフェルナンデス大
  • [Int'l Joint Research] ヒューストン大/ロズウェル癌研/ジョンズホプキンス大(米国)

    • Country Name
      U.S.A.
    • Counterpart Institution
      ヒューストン大/ロズウェル癌研/ジョンズホプキンス大
  • [Journal Article] Thermodynamics and Photodynamics of a Monoprotonated Porphyrin Directly Stabilized by Hydrogen Bonding with Polar Protic Solvents2017

    • Author(s)
      Suzuki Wataru、Kotani Hiroaki、Ishizuka Tomoya、Ohkubo Kei、Shiota Yoshihito、Yoshizawa Kazunari、Fukuzumi Shunichi、Kojima Takahiko
    • Journal Title

      Chemistry - A European Journal

      Volume: 23 Pages: 4669~4679

    • DOI

      10.1002/chem.201606012

    • Peer Reviewed / Int'l Joint Research
  • [Journal Article] Selective CO Production in Photoelectrochemical Reduction of CO2 with a Cobalt Chlorin Complex Adsorbed on Multi-Walled Carbon Nanotubes in Water2017

    • Author(s)
      Aoi, S.; Mase, K.; Ohkubo, K.; Suenobu, T.; Fukuzumi, S.
    • Journal Title

      ACS Energy Lett.

      Volume: 2 Pages: 印刷中

    • DOI

      10.1021/acsenergylett.6b00630

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Dihydroxylation of Styrene by Sodium Chlorite with Scandium Triflate2017

    • Author(s)
      Ohkubo, K.; Hirose, K.; Shibata, T.; Takamori, K.; Fukuzumi, S.
    • Journal Title

      J. Phys. Org. Chem.

      Volume: 30 Pages: 印刷中

    • DOI

      10.1002/poc.3619

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Exfoliation and Supramolecular Functionalization of Graphene with an Electron Donor Perylenediimide Derivative2017

    • Author(s)
      Martin-Gomis, L.; Karousis, N.; Fernandez-Lazaro, F.; Petsalakis, I. D.; Ohkubo, K.; Fukuzumi, S.; Tagmatarchis N. Sastre-Santos, A;.
    • Journal Title

      Photochem. Photobiol. Sci.

      Volume: 16 Pages: 印刷中

    • DOI

      10.1039/C6PP00351F

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Impact of Peripheral Substituents in Regioselective Synthesis of Position-10 or Position-20 Bromobacteriochlorins2017

    • Author(s)
      Joshi, P.; Ohkubo, K.; Dukh, M.; Tabaczynski, W.; Patel, N. J.; Missert, J. R.; Fukuzumi, S.; Pandey, R. K.
    • Journal Title

      Tetrahedron Lett.

      Volume: 58 Pages: 印刷中

    • DOI

      10.1016/j.tetlet.2017.01.044

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Synthetic Control over Intra- and Intermolecular Charge Transfer Can Turn on the Fluorescence Emission of Non-emissive Coumarin2016

    • Author(s)
      Jhun, B. H.; Ohkubo, K.; Fukuzumi, S.; You, Y.
    • Journal Title

      J. Mater. Chem. C

      Volume: 4 Pages: 4556-4567

    • DOI

      10.1039/C6TC00639F

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Photooxygenation of Alkanes by Dioxygen with p-Benzoquinone Derivatives with High Quantum Yields2016

    • Author(s)
      Ohkubo, K.; Hirose, K.; Fukuzumi, S
    • Journal Title

      Photochem. Photobiol. Sci.

      Volume: 8 Pages: 731-714

    • DOI

      10.1039/C6PP00102E

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Two-Phase Photocatalytic Oxidation of Toluene Derivatives by Dioxygen with 3-Cyano-1-decylquinolinium Ion2016

    • Author(s)
      Ohkubo, K.; Hirose, K.; Fukuzumi, S.
    • Journal Title

      RSC Adv.

      Volume: 6 Pages: 41011-41014

    • DOI

      10.1039/C6RA05993G

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Catalytic Reduction of Proton, Oxygen and Carbon Dioxide with Cobalt Macrocyclic Complexes2016

    • Author(s)
      Mase, K.; Aoi, S.; Ohkubo, K.; Fukuzumi, S.
    • Journal Title

      J. Porphyrins Phthalocyanines

      Volume: 20 Pages: 935-949

    • DOI

      10.1142/S1088424616300111

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Catalytic Hydroxylation of Benzene to Phenol by Dioxygen with an NADH Analog2016

    • Author(s)
      Hirose, K.; Ohkubo, K.; Fukuzumi, S.
    • Journal Title

      Chem.-Eur. J.

      Volume: 22 Pages: 12904-12909

    • DOI

      10.1002/chem.201602856

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Axially Substituted Silicon Phthalocyanine as Electron Donor in a Dyad and Triad with Azafullerene as Electron Acceptor for Photoinduced Charge Separation2016

    • Author(s)
      Rotas, G.; Martin-Gomis, L.; Ohkubo, K.; Fernandez-Lazaro, F.; Fukuzumi, S.; Tagmatarchis, N.; Sastre-Santos, A.
    • Journal Title

      Chem.-Eur. J.

      Volume: 22 Pages: 15137-15143

    • DOI

      10.1002/chem.201603065

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Reactivity of 2,2-Diphenyl-1-picrylhydrzyl Solubilized in Water by β-Cyclodextrin and Its Methylated Derivative2016

    • Author(s)
      Nakanishi, I.; Ohkubo, K.; Kamibayashi, M.; Ogawa, Y.; Ozawa, T.; Matsumoto, K.; Fukuzumi, S.
    • Journal Title

      Chem. Select

      Volume: 1 Pages: 3367-3370

    • DOI

      10.1002/slct.201600745

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Controllable Threshold Voltage in Organic Complementary Logic Circuits with an Electron-Trapping Polymer and Photoactive Gate Dielectric Layer2016

    • Author(s)
      Dao, T. T.; Sakai, H.; Nguyen, H. T.; Ohkubo, K.; Fukuzumi, S.; Murata, H.
    • Journal Title

      ACS Appl. Mater. Interfaces

      Volume: 8 Pages: 18249-18255

    • DOI

      10.1021/acsami.6b03183

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Synthetically Tuneable Biomimetic Artificial Photosynthetic Reaction Centres That Closely Resemble the Natural System in Purple Bacteria2016

    • Author(s)
      Lee, S.-H.; Blake, I. M.; Larsen, A. G.; McDonald, J. A.; Ohkubo, K.; Fukuzumi, S.; Reimers, J. R.; Crossley, M. J.
    • Journal Title

      Chem. Sci.

      Volume: 7 Pages: 6534-6550

    • DOI

      10.1039/C6SC01076H

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Photocatalytic Oxidation of Iron(II) Complexes by Dioxygen with 9-Mesityl-10-methylacridinium Ion2016

    • Author(s)
      Tsudaka, T.; Ohkubo, K.; Fukuzumi, S.
    • Journal Title

      Chem. Commun.

      Volume: 52 Pages: 6178-6180

    • DOI

      10.1039/C6CC00359A

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Photoinduced Electron Transfer in Porous Organic Salt Crystals Impregnated with Fullerenes2016

    • Author(s)
      Hasegawa, T.; Ohkubo, K.; Hisaki, I.; Miyata, M.; Tohnai, N.; Fukuzumi, S.
    • Journal Title

      Chem. Commun.

      Volume: 52 Pages: 7928-7931

    • DOI

      10.1039/C6CC02377K

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Aluminium Ion-Promoted Radical-Scavenging Reaction of Methylated Hydroquinone Derivatives2016

    • Author(s)
      Nakanishi, I.; Ohkubo, K.; Ogawa, Y.; Matsumoto, K.; Ozawa, T.; Fukuzumi, S.
    • Journal Title

      Org. Biomol. Chem.

      Volume: 14 Pages: 7956-7961

    • DOI

      10.1039/C6OB01470D

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Electrochemical Reduction of Cationic Li+@C60 to Neutral Li+@C60.-: Isolation and Characterisation of Endohedral [60]Fulleride2016

    • Author(s)
      Ueno, H.; Aoyagi, S.; Yamazaki, Y.; Ohkubo, K.; Ikuma, N.; Okada, H.; Kato, T.; Matsuo, Y.; Fukuzumi, S.; Kokubo, K.
    • Journal Title

      Chem. Sci.

      Volume: 7 Pages: 5770-5774

    • DOI

      10.1039/C6SC01209D

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] A Profluorescent Nitroxide Probe for Ascorbic Acid Detection and Its Application to Quantitative Analysis of Diabetic Rat Plasma2016

    • Author(s)
      Matsuoka, Y.; Ohkubo, K.; Yamasaki, T.; Yamato, M.; Ohtabu, H.; Shirouzu, T.; Fukuzumi, S.; Yamada, K.
    • Journal Title

      RSC. Adv.

      Volume: 6 Pages: 60907-60915

    • DOI

      10.1039/C6RA07693A

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Photocatalytic Reduction of CO2 and H2O to CO and H2 with a Cobalt Chlorin Complex Adsorbed on Multi-Walled Carbon Nanotubes2016

    • Author(s)
      Aoi, S.; Mase, K.; Ohkubo, K.; Fukuzumi, S.
    • Journal Title

      Catal. Sci. Technol.

      Volume: 6 Pages: 4077-4080

    • DOI

      10.1039/C6CY00376A

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Aromatic Monochlorination Photosensitized by DDQ with Hydrogen Chloride under Visible Light Irradiation2016

    • Author(s)
      Ohkubo, K.; Fujimoto, A.; Fukuzumi, S.
    • Journal Title

      Chem. Asian J.

      Volume: 11 Pages: 996-999

    • DOI

      10.1002/asia.201600083

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Photocatalytic Oxygenation of Substrates by Dioxygen with Protonated Manganese(III) Corrolazine2016

    • Author(s)
      Jung, J.; Neu, H. M.; Leeladee, P.; Siegler, M. A.; Ohkubo, K.; Goldberg, D. P.; Fukuzumi, S.
    • Journal Title

      Inorg. Chem.

      Volume: 55 Pages: 3218-3228

    • DOI

      10.1021/acs.inorgchem.5b02019

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Enhanced Electron-Transfer Reactivity of a Nonheme Iron(IV)-Imido Complex as Compared to the Iron(IV)-Oxo Analog2016

    • Author(s)
      Vardhaman, A. K.; Lee, Y.-M.; Jung, J.; Ohkubo, K.; Nam, W.; Fukuzumi, S.
    • Journal Title

      Angew. Chem., Int. Ed.

      Volume: 55 Pages: 3709-3713

    • DOI

      10.1002/anie.201600287

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] Photoinduced Processes of Supramolecular Nanoarrays Composed of Porphyrin and Benzo[ghi]perylenetriimide Units through Triple Hydrogen Bonds with One-Dimensional Columnar Phases2016

    • Author(s)
      Sakai, H.; Ohkubo, K.; Fukuzumi, S.; Hasobe, T.
    • Journal Title

      Chem. Asian J.

      Volume: 11 Pages: 613-624

    • DOI

      10.1002/asia.201501367

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] The Effect of Metallation on Porphyrin-Based Bifunctional Agents in Tumor-Imaging and Photodynamic Therapy2016

    • Author(s)
      Patel, N. J.; Chen, Y.; Joshi, P.; Pera, P.; Baumann, H.; Missert, J. R.; Ohkubo, K.; Fukuzumi, S.; Nani, R. R.; Schnermann, M. J.; Chen, P.; Zhu, J.; Kadish, K. M.; Pandey, R. K.
    • Journal Title

      Bioconjugate Chem.

      Volume: 27 Pages: 667-680

    • DOI

      10.1021/acs.bioconjchem.5b00656

    • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
  • [Journal Article] An Amphoretic Reactivity of a Mixed-Valent Bis(μ-oxo)dimanganese(III,IV) Complex Acting as an Electrophile and a Nucleophile2016

    • Author(s)
      Sankaralingam, M.; Jeon, S. H.; Lee, Y.-L.; Seo, M. S.; Ohkubo, K.; Fukuzumi, S.; Nam, W.
    • Journal Title

      Dalton Trans.

      Volume: 27 Pages: 376-383

    • DOI

      10.1039/C5DT04292E

    • Peer Reviewed / Open Access / Int'l Joint Research / Acknowledgement Compliant
  • [Presentation] 二酸化塩素ラジカルを用いた光酸素化反応2017

    • Author(s)
      大久保敬
    • Organizer
      日本化学会 第97春季年会
    • Place of Presentation
      慶応大
    • Year and Date
      2017-03-16 – 2017-03-19
  • [Presentation] 超高難易度酸化反応を可能にする光触媒2016

    • Author(s)
      大久保敬
    • Organizer
      有機光化学研究会
    • Place of Presentation
      あわら市
    • Year and Date
      2016-12-01 – 2016-12-02
  • [Presentation] 亜塩素酸ナトリウムを用いたスチレンの水酸化反応2016

    • Author(s)
      大久保敬
    • Organizer
      第49回酸化反応討論会
    • Place of Presentation
      徳島大
    • Year and Date
      2016-11-12 – 2016-11-13
  • [Presentation] One-step Aerobic Oxygenation of Hydrocarbons by Electron Transfer2016

    • Author(s)
      Ohkubo, Kei
    • Organizer
      PRiME2016
    • Place of Presentation
      ホノルル
    • Year and Date
      2016-10-02 – 2016-10-06
    • Int'l Joint Research / Invited
  • [Presentation] リチウムイオン内包フラーレンとペプチドポルフィリンの超分子内光電荷分離2016

    • Author(s)
      大久保敬
    • Organizer
      2016年光化学討論会
    • Place of Presentation
      東京大学
    • Year and Date
      2016-09-06 – 2016-09-08
  • [Presentation] ベンゾキノンの光励起状態を用いたアルカンの酸素酸化反応2016

    • Author(s)
      大久保敬
    • Organizer
      第27回基礎有機化学討論会
    • Place of Presentation
      広島
    • Year and Date
      2016-09-01 – 2016-09-03
  • [Presentation] Supramolecular Electron-Transfer Chemistry of Li+@C60 with Porphyrinoids2016

    • Author(s)
      Ohkubo, Kei
    • Organizer
      International Conference on Porphyrins and Phthalocyanines
    • Place of Presentation
      南京
    • Year and Date
      2016-07-03 – 2016-07-08
    • Int'l Joint Research
  • [Presentation] ベンゾキノンの光励起状態を用いたアルカンの酸化反応2016

    • Author(s)
      大久保敬
    • Organizer
      第40回有機電子移動化学討論会
    • Place of Presentation
      新潟大学
    • Year and Date
      2016-06-23 – 2016-06-24
  • [Presentation] Multiple photosynthetic reaction centers of porphyrinic polypeptide-Li+@C60 supramolecular complexes2016

    • Author(s)
      Ohkubo, Kei
    • Organizer
      229th ECS MEETING - ECS - The Electrochemical Society
    • Place of Presentation
      サンディエゴ
    • Year and Date
      2016-05-31 – 2016-06-04
    • Int'l Joint Research / Invited
  • [Presentation] ONE-STEP OXYGENATION OF ALKANES PHOTOSENSITIZED BY BENZOQUINONE DERIVATIVES2016

    • Author(s)
      Ohkubo, Kei
    • Organizer
      The 26th IUPAC Symposium on Photochemistry
    • Place of Presentation
      大阪
    • Year and Date
      2016-04-03 – 2016-04-08
    • Int'l Joint Research / Invited
  • [Patent(Industrial Property Rights)] ポリマー成形体2016

    • Inventor(s)
      大久保敬・井上豪・高森清人
    • Industrial Property Rights Holder
      大久保敬・井上豪・高森清人
    • Industrial Property Rights Type
      特許
    • Industrial Property Number
      特願 2016-244690
    • Filing Date
      2016-12-16

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Published: 2018-12-17   Modified: 2022-02-22  

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