Development of catalysts devices for selective oxidation of hydrocabons with O_2

• Project/Area Number: 20360367
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Catalyst/Resource chemical process
• Research Institution: Kanagawa University
• Principal Investigator: HIKICHI Shiro Kanagawa University, 工学部, 教授 (10282857)
• Co-Investigator(Renkei-kenkyūsha): NAKAZAWA Jun 神奈川大学, 工学部, 特別助手 (70550888)
• Project Period (FY): 2008 – 2010
• Project Status: Completed (Fiscal Year 2010)
• Budget Amount: ¥19,110,000 (Direct Cost: ¥14,700,000、Indirect Cost: ¥4,410,000); Fiscal Year 2010: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2009: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000); Fiscal Year 2008: ¥14,170,000 (Direct Cost: ¥10,900,000、Indirect Cost: ¥3,270,000)
• Keywords: 酸化反応 / 錯体触媒 / 固定化錯体触媒 / 酸素活性化 / 過酸化物 / ニッケル / 鉄 / 炭化水素 / 酸素 / コバルト / Bio-inspired触媒

Research Abstract

Novel homogeneous and heterogeneous catalysts for biomimetic hydrocarbon oxidation process have been developed. Tuning the electronic property of the ligand of the nickel complex catalyst leads to achieve selective hydroxylation of alkane with organic peroxide. A thiophenolate complex of nickel(II) activates 02 through intramolecular electron transfer from sulfer donor ligand to the nickel center. Also, novel immobilized metallocomplex catalysts based on the ligand mimicking the metal-supporting motifs found in the active site of the enzymes have been developed. The iron complex-immobilized catalysts exhibit the catalysis for hydrocarbon oxygenation with aqueous H202 at ambient temperature.

Research Products

• [Journal Article] (2010)
  • Author(s): Shiro Hikichi, Koyu Fujita, Yoshitaka Manabe, Munetaka Akita, Jun Nakazawa, Hidehito Komatsuzaki
  • Journal Title: Eur.J.Inorg.Chem. Pages: 5529-5537
  • Peer Reviewed
• [Journal Article] Tuning the Stability and Reactivity of Metal-bound Alkylperoxide by Remote Site Substitution of the Ligand (2010)
  • Author(s): Shiro Hikichi, Chiho Kobayashi, Michito Yoshizawa, Munetaka Akita
  • Journal Title: Chem.Asian J. Vol.5 Pages: 2086-2092
  • Peer Reviewed
• [Journal Article] 人工酵素の開発を目指した錯体触媒の分子設計 (2010)
  • Author(s): 引地史郎,中澤順
  • Journal Title: 触媒 Vol.52,No.4 Pages: 243-248
• [Journal Article] Tuning the Stability and Reactivity of Metal-bound Alkylperoxide by Remote Site Substitution of the Ligand (2010)
  • Author(s): S.Hikichi, C.Kobayashi, M.Yoshizawa, M.Akita
  • Journal Title: Chem.Asian J. Volume: 5 Pages: 2086-2092
  • Peer Reviewed
• [Journal Article] Coordination property of organoborate ligands : Steric hindrance around distal boron center direct the conformation of dialkylbis(imidazolyl)borate scaffold (2010)
  • Author(s): S.Hikichi, K.Fujita, Y.Manabe, M.Akita, J.Nakazawa, H.Komatsuzaki
  • Journal Title: Eur.J.Inorg.Chem. Pages: 5529-5537
  • Peer Reviewed
• [Journal Article] Design, Synthesis, and Catalysis of Bio-inspired Immobilized Metallocomplex Catalyst (2009)
  • Author(s): Shiro Hikichi, Mami Kaneko, Yasuyuki Miyoshi, Noritaka Mizuno, Koyu Fujita, Munetaka Akita
  • Journal Title: Top.Catal. Vol.52 Pages: 845-851
  • Peer Reviewed
• [Journal Article] Acetoxybis(imidazolyl)methylborate [B(Im^<N-Me>)_2(OC(=O)Me)Me]^- : Carboxylation of borane moiety of imidazolyl-based scorpionate (2009)
  • Author(s): Koyu Fujita, Munetaka Akita, Shiro Hikichi
  • Journal Title: Inorg.Chim.Acta Vol.362 Pages: 4472-4479
  • Peer Reviewed
• [Journal Article] Structural Characterization and Oxidation Activity of a Nickel(II) Alkylperoxo Complex (2009)
  • Author(s): Shiro Hikichi, Hideho Okuda, Yoshiko Ohzu, Munetaka Akita
  • Journal Title: Angew.Chem.Int.Ed. Vol.52 Pages: 188-191
  • Peer Reviewed
• [Journal Article] Design, Synthesis, and Catalysis of Bio-inspired Immobilized Metallocomplex Catalyst (2009)
  • Author(s): S.Hikichi, M.Kaneko, Y.Miyoshi, N.Mizuno, K.Fujita, M.Akita
  • Journal Title: Topics in Catalysis 52 Pages: 845-851
  • Peer Reviewed
• [Journal Article] Acetoxybis(imidazolyl)methylborate[B(Im^<N-Me>)_2(OC(=O)Me)Me]^-: Carboxylation of borane moiety of imidazolyl-based scorpionate (2009)
  • Author(s): K.Fujita, M.Akita, S.Hikichi
  • Journal Title: Inorg.Chim.Acta 362 Pages: 4472-4479
  • Peer Reviewed
• [Journal Article] Structural Characterization and Oxidation Activity of a Nickel (II) Alkylperoxo Complex. (2009)
  • Author(s): S. Hikichi, H. Okuda, Y. Ohzu, M. Akita
  • Journal Title: Angew. Chem. Int. Ed. 48 Pages: 188-191
  • Peer Reviewed
• [Journal Article] Design, Synthesis, and Catalysis of Bio-inspired Immobilized Metallocomplex Catalyst. (2009)
  • Author(s): S. Hikichi, M. Kaneko, Y. Miyoshi, N Mizuno K Fujita M Akita
  • Journal Title: Topics in Catalysis (印刷中)
  • Peer Reviewed
• [Journal Article] Tuning the Stability and Reactivity of Metal-bound Alkylperoxide by Remote Site Substitution of the Ligand
  • Author(s): S.Hikichi, C.Kobayashi, M.Yoshizawa, M.Akita
  • Journal Title: Chem.Asian J. (印刷中)
  • Peer Reviewed
• [Presentation] Design of bio-inspired homogeneous and heterogeneous oxidation catalysts (2010)
  • Author(s): 引地史郎
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies (Pasifichem 2010)
  • Place of Presentation: Honolulu, Hawaii, U.S.A.(招待講演)
  • Year and Date: 2010-12-19
• [Presentation] Design of bio-inspired homogeneous and heterogeneous oxidation catalysts (2010)
  • Author(s): Shiro Hikichi
  • Organizer: 2010 International Chemical Congress of Pacific Basin Societies (Pasifichem 2010)
  • Place of Presentation: Hilton Hawaiian Village (Honolulu, Hawaii, U.S.A.)
  • Year and Date: 2010-12-19
• [Presentation] Design of bio-inspired oxidation catalysts : Tuning the substrate oxidizing activity of nickel-oxygen complexes (2010)
  • Author(s): 引地史郎, 中澤順
  • Organizer: The 5th Asian Biological Inorganic Chemistry Conference
  • Place of Presentation: Kaohsiung, Taiwan(招待講演)
  • Year and Date: 2010-11-03
• [Presentation] Design of bio-inspired oxidation catalysts : Tuning the substrate oxidizing activity of nickel-oxygen complexes (2010)
  • Author(s): Shiro Hikichi, Jun Nakazawa
  • Organizer: The 5th Asian Biological Inorganic Chemistry Conference
  • Place of Presentation: The Ambassador Hotel (Kaohsiung, Taiwan)
  • Year and Date: 2010-11-03
• [Presentation] Bio-inspired酸化触媒の開発を目指して-分子設計とナノ構造制御- (2010)
  • Author(s): 引地史郎
  • Organizer: 第106回触媒討論会
  • Place of Presentation: 甲府市(山梨大学)(招待講演)
  • Year and Date: 2010-09-17
• [Presentation] Bio-inspired酸化触媒の開発を目指して-分子設計とナノ構造制御- (2010)
  • Author(s): 引地史郎
  • Organizer: 第106回触媒討論会
  • Place of Presentation: 山梨大学(山梨県)
  • Year and Date: 2010-09-17
• [Presentation] 新規ボレート配位子の開発と固定化錯体触媒への展開 (2010)
  • Author(s): 引地史郎
  • Organizer: 日本化学会第4回関東支部大会
  • Place of Presentation: つくば市(筑波大学)(招待講演)
  • Year and Date: 2010-08-30
• [Presentation] 新規ボレート配位子の開発と固定化錯体触媒への展開 (2010)
  • Author(s): 引地史郎
  • Organizer: 日本化学会第4回関東支部大会
  • Place of Presentation: 筑波大学(茨城県)
  • Year and Date: 2010-08-30
• [Presentation] アルカン水酸化活性の向上を目指したニッケルおよびコバルト錯体触媒の分子設計 (2009)
  • Author(s): 中澤順,奥田秀穂,引地史郎
  • Organizer: 第104回触媒討論会
  • Place of Presentation: 宮崎市(宮崎大学)(招待講演)
  • Year and Date: 2009-09-30
• [Presentation] Bio-inspired alkane oxidation catalysts based on nickel complexes (2009)
  • Author(s): Shiro Hikichi, Hideho Okuda, Naoki Imamura, Akiyoshi Ishii, Jun Nakazawa
  • Organizer: 14th International Conference on Biological Inorganic Chemistry
  • Place of Presentation: 名古屋市(名古屋国際会議場)
  • Year and Date: 2009-07-28
• [Presentation] Bio-inspired alkane oxidation catalysts based on nickel complexes (2009)
  • Author(s): S.Hikichi, H.Okuda, N.Imamura, Y.Ishii, J.Nakazawa
  • Organizer: 14th International Conference on Biological Inorganic Chemistry
  • Place of Presentation: 名古屋国際会議場
  • Year and Date: 2009-07-28
• [Presentation] ニソケル錯体触媒のアルカン酸化活性の検討 (2008)
  • Author(s): 奥田秀穂,引地史郎
  • Organizer: 第41回酸化反応討論会
  • Place of Presentation: 福岡市(九州大学)
  • Year and Date: 2008-11-28
• [Presentation] コバルト(II)セミキノナート錯体によるbio-inspired酸素酸化触媒反応系の構築 (2008)
  • Author(s): 池田篤司, 瀬川卓磨, 星野一也, 引地史郎
  • Organizer: 第41回酸化反応討論会
  • Place of Presentation: 九州大学(福岡)
  • Year and Date: 2008-11-28
• [Presentation] チオール修飾シリカを担体とする固定化錯体触媒の調製 (2008)
  • Author(s): 引地史郎,金子真実,名畑実有子
  • Organizer: 第102回触媒討論会
  • Place of Presentation: 名古屋市(名古屋大学)
  • Year and Date: 2008-09-25
• [Remarks] ホームページ等
  • URL: http://apchem2.kanagawa-u.ac.jp/~hikichilab/index.html
• [Remarks]
  • URL: http://apchem2.kanagawa-u.ac.jp/~hikichilab/index.html
• [Remarks]
  • URL: http://apchem2.kanagawa-u.ac.jp/~hikichilab/index.html
• [Remarks]
  • URL: http://apchem2.kanagawa-u.ac.jp/~hikichilab/index.html