Creation of metal complexes that utilize naturally abundant calcogen source as reactants in synthetic chenistry

• Project/Area Number: 23350027
• Research Category: Grant-in-Aid for Scientific Research (B)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Osaka University
• Principal Investigator: SUGIMOTO Hideki 大阪大学, 工学(系)研究科(研究院), 准教授 (00315970)
• Project Period (FY): 2011-04-01 – 2014-03-31
• Project Status: Completed (Fiscal Year 2013)
• Budget Amount: ¥19,500,000 (Direct Cost: ¥15,000,000、Indirect Cost: ¥4,500,000); Fiscal Year 2013: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2012: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2011: ¥10,660,000 (Direct Cost: ¥8,200,000、Indirect Cost: ¥2,460,000)
• Keywords: ルテニウム / オスミウム / モリブデン / タングステン / 硫黄 / セレン / 過酸化水素 / 金属錯体 / 酸素 / 硫黄錯体

Research Abstract

We examined reactions of metal complexes with naturally abundant chalcogen source and catalytic reactions in atom transfer between substrates and the chalcogen source. Mononuclear ruthenium(II) complexes having nitrogen containing tetradentate ligands were synthesized and employed as a catalyst in sulfur atom transfer from inorganic sulfur and norbornen. Mononuclear molybdenum and tungsten complexes having one terminal sulfide or selenido group were prepared as models of molybdenum and tungsten enzyme active sites, where hydrogensulfide and hydrogenselenide ions were used. Their atom transfer reactivity to triphenylphosphines was investigated. Mononuclear osmium complexes with nitrogen containing tetradentate ligands were synthesized and were revealed to catalyze 1,2-dyhydroxylation of alkenes with hydrogen peroxide.

Research Products

• [Journal Article] (2013)
  • Author(s): H. Sugimoto, S. Tatemoto, K. Toyota, K. Ashikari, M. Kubo, T. Ogura, S. Itoh
  • Journal Title: Chem. Comm Volume: 43 Pages: 4358-4360
• [Journal Article] (2013)
  • Author(s): H. Sugimoto, K. Hatakeda, K. Toyota, S. Tatemoto, M. Kubo, T. Ogura, S. Itoh
  • Journal Title: Dalton Trans Volume: 42 Pages: 3059-3070
• [Journal Article] (2013)
  • Author(s): H. Sugimoto, K. Ahikari, S. Itoh
  • Journal Title: Inorg. Chem Volume: 52 Pages: 543-545
• [Journal Article] (2013)
  • Author(s): H. Sugimoto, K. Ashikari, S. Itoh
  • Journal Title: Chem. Asian J Volume: 8 Pages: 2154-2160
• [Journal Article] Oxo-sulfido- and oxo-selenido-molybdenum(VI) complexes possessing dithiolene ligand related to the active sites of hydroxylases of molybdoenzymes: Low temperature preparation and characterisation (2013)
  • Author(s): Shinobu Itoh, et al.
  • Journal Title: Chem. Commun. Volume: 49 Issue: 39 Pages: 4358-4360
  • DOI: 10.1039/c2cc35345h
  • Peer Reviewed / Open Access
• [Journal Article] A new series of bis(ene-1,2-dithiolato)tungsten(IV), -(V), -(VI) complexes as reaction centre models of tungsten enzymes: Preparation, crystal structures and spectroscopic properties (2013)
  • Author(s): Hideki Sugimoto, Kohei Hatakeda, Kazuo Toyota, Susumu Tatemoto, Minoru Kubo, Takashi Ogura, Shinobu Itoh
  • Journal Title: Dalton Transactions Volume: 42 Pages: 3059-3070
  • Peer Reviewed
• [Journal Article] C–H Bond Activation of the Supporting Ligand in an Osmium(III) Complex with H2O2: Formation of an Organometallic Osmium(IV) Complex (2013)
  • Author(s): Shinobu Itoh, et al.
  • Journal Title: Inorg. Chem. Volume: 52 Issue: 2 Pages: 543-545
  • DOI: 10.1021/ic302169k
  • Peer Reviewed / Open Access
• [Journal Article] Osmium(III) and Osmium(V) Complexes Bearing a Macrocyclic Ligand: A Simple and Efficient Catalytic System for cis-Dihydroxylation of Alkenes with Hydrogen Peroxide (2013)
  • Author(s): Hideki Sugimoto, Kenji Ashikari, Shinobu Itoh
  • Journal Title: Chemistry An Asian Journal Volume: 8 Issue: 9 Pages: 2154-2160
  • DOI: 10.1002/asia.201300329
  • Peer Reviewed / Open Access
• [Journal Article] Oxo-carboxylato-molybdenum(VI) complexes possessing dithiolene ligand related to the active site of type II class of DMSOR family of molybdoenzymes (2013)
  • Author(s): Shinobu Itoh, et al.
  • Journal Title: Dalton Trans. Volume: 42 Issue: 45 Pages: 15927-15930
  • DOI: 10.1039/c3dt51485d
  • Peer Reviewed
• [Journal Article] A new series of bis(ene-1,2-dithiolato)tungsten(IV), -(V), -(VI) complexes as reaction centre models of tungsten enzymes: preparation, crystal structures and spectroscopic properties (2013)
  • Author(s): Shinobu Itoh, et al.
  • Journal Title: Dalton Trans. Volume: 42 Issue: 9 Pages: 3059-3070
  • DOI: 10.1039/c2dt32179c
  • Peer Reviewed / Open Access
• [Journal Article] (2012)
  • Author(s): H. Sugimoto, K. Kitayama, S. Mori, S. Itoh, J. Am
  • Journal Title: Chem. Soc Volume: 134 Pages: 19270-19280
• [Journal Article] (165) An Osmium(III)/Osmium(V) Redox Couple Generating OsV(O)(OH) Center for cis-1,2-Dihydroxylation of Alkenes with H2O2: Os Complex with a Nitrogen- based Tetradentate Ligand (2012)
  • Author(s): Shinobu Itoh, et al.
  • Journal Title: J Am. Chem. Soc. Volume: 134 Issue: 46 Pages: 19270-19280
  • DOI: 10.1021/ja309566c
  • Peer Reviewed
• [Journal Article] Heterolytic Alkylhydroperoxide O-O Bond Cleavage by Copper(I) Complexes (2012)
  • Author(s): Tetsuro Tano
  • Journal Title: Eur. J. Inorg. Chem. Volume: 2012 Issue: 26 Pages: 4099-4103
  • DOI: 10.1002/ejic.201200555
  • Peer Reviewed
• [Journal Article] (2011)
  • Author(s): H. Sugimoto, H. Tano, K. Suyama, T. Kobayashi, H. Miyake, S. Itoh, R. P. Mtei, M. L. Kirk
  • Journal Title: Dalton Trans Volume: 40 Pages: 1119-1131
• [Journal Article] (2011)
  • Author(s): ・H. Sugimoto, H. Tano, H. Miyake, S. Itoh
  • Journal Title: Dalton Trans Volume: 40 Pages: 2358-2365
• [Journal Article] (2011)
  • Author(s): H. Sugimoto, K. Kitayama, K. Ashikari, C. Matsunami, N. Ueda, K. Umakoshi, Y. Hosokoshi, Y. Sasaki, S. Itoh
  • Journal Title: Inorg. Chem Volume: 50 Pages: 9014-9023
• [Journal Article] (2011)
  • Author(s): H. Sugimoto, R. Tajima, K. Toyota, H. Miyake, S. Itoh
  • Journal Title: Chem. Lett Volume: 40 Pages: 1146-1148
• [Journal Article] (2011)
  • Author(s): H. Sugimoto, M. Z. Ertem, S. Yamaguchi, A. Kunishita, H. Sugimoto, N. Fujieda, T. Ogura, C. J. Cramer, S. Itoh
  • Journal Title: Dalton Trans Volume: 40 Pages: 10326-10336
• [Presentation] 含窒素四座配位子を有するオスミウム錯体を用いたアルケンの1,2-アミノヒドロキシル化反応 (2014)
  • Author(s): 杉本秀樹、三上明音、伊東忍
  • Organizer: 日本化学会春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] 窒素系4座配位子を用いたオスミウム錯体の構造制御 (2014)
  • Author(s): 前田和紀、杉本秀樹、伊東忍
  • Organizer: 日本化学会春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] DMSORファミリー活性中心のモデル錯体としてのオキソ-アルコラトモリブデン(VI)錯体の合成と性質 (2014)
  • Author(s): 佐藤正典、杉本秀樹、朝野香織、鈴木健之、伊東忍
  • Organizer: 日本化学会春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] (2013)
  • Author(s): 三上明音, 杉本秀樹, 伊東忍
  • Organizer: 第63回錯体化学討論会
  • Place of Presentation: 琉球大学
• [Presentation] (2013)
  • Author(s): 佐藤正典, 杉本秀樹, 伊東忍
  • Organizer: 第63回錯体化学討論会
  • Place of Presentation: 琉球大学
• [Presentation] (2013)
  • Author(s): 前田和紀, 杉本秀樹, 伊東忍
  • Organizer: 第94回春季年会
  • Place of Presentation: 筑波大学
• [Presentation] (2013)
  • Author(s): 杉本秀樹 ,芦刈健治, 三上明音, 伊東忍
  • Organizer: 第94回春季年会
  • Place of Presentation: 筑波大学
• [Presentation] (2013)
  • Author(s): 金武孝幸, 杉本秀樹, 伊東忍
  • Organizer: 第94回春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] (2013)
  • Author(s): 佐藤正典, 杉本秀樹, 伊東忍
  • Organizer: 第94回春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] (2013)
  • Author(s): 前田和紀, 杉本秀樹, 伊東忍
  • Organizer: 第94回春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] (2013)
  • Author(s): 三上明音, 杉本秀樹, 伊東忍
  • Organizer: 第94回春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] An Osmium(III)/Osmium(V) Redox Couple for cis-1,2-Dihydroxylation of Alkens with H2O2 (2013)
  • Author(s): Hideki Sugimoto
  • Organizer: The Sixteenth International Symposium on Relations between Homogeneous and Heterogeneous Catalysis
  • Place of Presentation: Hokkaido University
• [Presentation] 六配位オキソモリブデン(VI)錯体の合成と反応性 (2013)
  • Author(s): 佐藤正典、杉本秀樹、伊東忍
  • Organizer: 錯体化学討論会
  • Place of Presentation: 琉球大学
• [Presentation] 環状四座配位子を持つオスミウム五価錯体によるアルケンの触媒的酸化反応 (2013)
  • Author(s): 杉本秀樹、芦刈健治、三上明音、伊東忍
  • Organizer: 酸化反応討論会
  • Place of Presentation: 筑波大学
• [Presentation] オスミウム(III)/(V)レドックスを利用するアルケンの選択的シスジオール化反応 (2012)
  • Author(s): 杉本秀樹
  • Organizer: 第43回中部化学関係協会支部連合秋季大会
  • Place of Presentation: 名古屋工業大学(招待講演)
  • Year and Date: 2012-11-10
• [Presentation] (2012)
  • Author(s): 杉本秀樹
  • Organizer: 第43回中部化学関係学協会支部連合秋季大会
  • Place of Presentation: 名古屋工業大学
• [Presentation] (2012)
  • Author(s): 畠田康平 ,杉本秀樹, 伊東忍
  • Organizer: 日本化学会第92回春季年会
  • Place of Presentation: 慶応義塾大学
• [Presentation] (2012)
  • Author(s): 芦刈健治, 杉本秀樹, 伊東忍
  • Organizer: 日本化学会第92回春季年会
  • Place of Presentation: 慶応義塾大学
• [Presentation] (2012)
  • Author(s): 三上明音, 杉本秀樹, 伊東忍
  • Organizer: 日本化学会第92回春季年会
  • Place of Presentation: 慶応義塾大学
• [Presentation] (2012)
  • Author(s): 妻鳥友樹, 杉本秀樹, 伊東忍
  • Organizer: 日本化学会第92回春季年会
  • Place of Presentation: 慶応義塾大学
• [Presentation] (2012)
  • Author(s): 森聖治, 杉本秀樹, 伊東忍
  • Organizer: 第62回錯体化学討論会
  • Place of Presentation: 富山大学
• [Presentation] (2012)
  • Author(s): 芦刈健治, 杉本秀樹, 伊東忍
  • Organizer: 第62回錯体化学討論会
  • Place of Presentation: 富山大学
• [Presentation] (2012)
  • Author(s): 三上明音, 杉本秀樹, 伊東忍
  • Organizer: 第62回錯体化学討論会
  • Place of Presentation: 富山大学
• [Presentation] (2012)
  • Author(s): 芦刈健治, 杉本秀樹, 伊東忍
  • Organizer: 第45回酸化反応討論会
  • Place of Presentation: 名古屋市立大学
• [Presentation] (2012)
  • Author(s): 芦刈健治, 三上明音, 杉本秀樹, 伊東忍
  • Organizer: 日本化学会第93回春季年会
  • Place of Presentation: 立命館大学
• [Presentation] (2012)
  • Author(s): 前田和紀, 杉本秀樹, 伊東忍
  • Organizer: 日本化学会第93回春季年会
  • Place of Presentation: 立命館大学
• [Presentation] (2012)
  • Author(s): 佐藤正典, 杉本秀樹, 伊東忍
  • Organizer: 日本化学会第93回春季年会
  • Place of Presentation: 立命館大学
• [Presentation] (2011)
  • Author(s): H. Sugimoto, K. Kitayama, S. Itoh
  • Organizer: 第61回錯体化学討論会
  • Place of Presentation: 岡山理科大学
• [Presentation] (2011)
  • Author(s): 畠田康平, 杉本秀樹, 久保稔, 倉尚志, 伊東忍
  • Organizer: 第6回錯体化学討論会
  • Place of Presentation: 岡山理科大学
• [Presentation] (2011)
  • Author(s): 樋口亮史, 杉本秀樹, 伊東忍
  • Organizer: 第61回錯体化学討論会
  • Place of Presentation: 岡山理科大学
• [Presentation] (2011)
  • Author(s): 芦刈健治 ,杉本秀樹, 伊東忍
  • Organizer: 第61回錯体化学討論会
  • Place of Presentation: 岡山理科大学
• [Presentation] (2011)
  • Author(s): 芦刈健治, 杉本秀樹, 伊東忍
  • Organizer: 第44回酸化反応討論会
  • Place of Presentation: 大阪大学