Development of nitrite reduction cycle on dinuclear complexes

• Project/Area Number: 17K05813
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Nagasaki University
• Principal Investigator: ARIKAWA Yasuhiro 長崎大学, 工学研究科, 准教授 (30346936)
• Project Period (FY): 2017-04-01 – 2020-03-31
• Project Status: Completed (Fiscal Year 2019)
• Budget Amount: ¥4,940,000 (Direct Cost: ¥3,800,000、Indirect Cost: ¥1,140,000); Fiscal Year 2019: ¥1,560,000 (Direct Cost: ¥1,200,000、Indirect Cost: ¥360,000); Fiscal Year 2018: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000); Fiscal Year 2017: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 亜硝酸イオン / 還元サイクル / ニトリド / アンモニア / 金属酵素 / 二核錯体 / ピラゾリルボラト / ルテニウム / 配位子交換反応 / アセトニトリル / イソチオシアネート / 一酸化窒素 / 合成化学 / 還元反応

Outline of Final Research Achievements

We achieved a stepwise nitrite (NO2-) reduction cycle based on a dinuclear ruthenium complex. This cycle means conversion of nitrite to NH3 and two H2O using six electrons and seven protons (NO2- + 7 H+ + 6e- -> NH3 + 2 H2O), demonstrating the reproduction of the function of nitrite reductase.
In this cycle, an unique bent-type nitride-bridged dinuclear complex was isolated. Ligand exchange reactions of its complex were also investigated.

Academic Significance and Societal Importance of the Research Achievements

微生物による自然界での窒素循環サイクルでは、空気中にほぼ無尽蔵に存在する窒素分子が形を変えて循環しており、アミノ酸等に含まれる窒素原子の究極的な原料は空気中の窒素分子であるため、生物にとって必須のサイクルである。このサイクルの中に亜硝酸還元酵素が含まれており、亜硝酸イオンをアンモニアまで還元している。これは、富栄養化の軽減などに関連しており、非常に重要な反応である。この反応を、人工的に金属錯体を使って再現した。

Research Products

• [Journal Article] Arrangement of a NO ligand and the neighboring sulfur-containing species on a dinuclear ruthenium complex by ligand substitution and linkage isomerism of a dimethyl sulfoxide ligand (2019)
  • Author(s): Yasuhiro Arikawa, Yuji Otsubo, Tomofumi Nakayama, Naoto Mitsuda, Shinnosuke Horiuchi, Eri Sakuda, Keisuke Umakoshi
  • Journal Title: Inorganica Chimica Acta Volume: 490 Pages: 45-50
  • DOI: 10.1016/j.ica.2019.02.036
  • NAID: 120006987773
  • Peer Reviewed
• [Journal Article] Synthetic NO reduction cycle on a bis(pyrazolato)-bridged dinuclear ruthenium complex including photo-induced transformation (2018)
  • Author(s): Arikawa Yasuhiro、Hiura Junko、Tsuchii Chika、Kodama Mika、Matsumoto Naoki、Umakoshi Keisuke
  • Journal Title: Dalton Transactions Volume: 印刷中 Issue: 22 Pages: 7399-7401
  • DOI: 10.1039/c8dt01208c
  • NAID: 120006987972
  • Peer Reviewed
• [Journal Article] Nitrite Reduction Cycle on a Dinuclear Ruthenium Complex Producing Ammonia (2018)
  • Author(s): Arikawa Yasuhiro、Otsubo Yuji、Fujino Hiroki、Horiuchi Shinnosuke、Sakuda Eri、Umakoshi Keisuke
  • Journal Title: Journal of the American Chemical Society Volume: 140 Issue: 2 Pages: 842-847
  • DOI: 10.1021/jacs.7b12020
  • Peer Reviewed
• [Presentation] 硫黄の酸化物およびオキソアニオンが架橋した二核ルテニウム錯体の合成および反応性 (2020)
  • Author(s): 吉田 研志良・辻田 佑介・有川 康弘・堀内 新之介・作田 絵里・馬越 啓介
  • Organizer: 日本化学会第100春季年会
• [Presentation] Synthetic Nitrite Reduction Cycle on a Ruthenium Complex Producing Ammonia (2019)
  • Author(s): Yasuhiro Arikawa
  • Organizer: The 24th Joint Seminar of the Kyushu Branch of the CSJ and the Busan Branch of KCS
  • Int'l Joint Research / Invited
• [Presentation] Theoretical Study on a Mechanism of Nitrite Reduction on a Diruthenium Platform (2019)
  • Author(s): Akihito Egi, Kei Ikeda, Hiromasa Tanaka, Yoshihito Shiota,Yasuhiro Arikawa, Kazunari Yoshizawa
  • Organizer: 15th International Symposium on Applied Bioinorganic Chemistry (ISABC15)
  • Int'l Joint Research
• [Presentation] Theoretical Study on a Mechanism of Nitrite Reduction on a Diruthenium Platform (2019)
  • Author(s): Akihito Egi, Kei Ikeda, Hiromasa Tanaka, Yoshihito Shiota,Yasuhiro Arikawa, Kazunari Yoshizawa
  • Organizer: 66th Symposium on Organometallic Chemistry
• [Presentation] インターカルコゲン化合物が架橋した二核ルテニウム錯体の合成および反応性 (2019)
  • Author(s): 辻田 佑介, 長岡 拓弥, 竹本 頌子, 有川 康弘, 堀内 新之介, 作田 絵里, 馬越 啓介
  • Organizer: 錯体化学会 第69回討論会
• [Presentation] 二核ルテニウム錯体を用いた亜硝酸イオン還元サイクル (2019)
  • Author(s): 有川 康弘
  • Organizer: 九州錯体化学懇談会５０周年記念シンポジウム
  • Invited
• [Presentation] カルコゲン間化合物が架橋した二核ルテニウム錯体の合成および反応性 (2019)
  • Author(s): 辻田 佑介・長岡 拓弥・竹本 頌子・有川 康弘・堀内 新之介・作田 絵里・馬越 啓介
  • Organizer: 日本化学会第99春季年会
• [Presentation] Theoretical Study on the Reduction of Nitrite to Ammonia on a Diruthenium Complex (2019)
  • Author(s): Akihito Egi, Kei Ikeda, Hiromasa Tanaka, Yoshihito Shiota,Yasuhiro Arikawa, Kazunari Yoshizawa
  • Organizer: 日本化学会第99春季年会
• [Presentation] Preparation and Reactivities of a cis-1,2 End-On Sulfur Monoxido Bridged Dinuclear Ruthenium Complex (2018)
  • Author(s): Y. Arikawa, T. Nagaoka, N. Takemoto, S. Horiuchi, E. Sakuda, and K. Umakoshi
  • Organizer: 65th Symposium on Organometallic Chemistry
• [Presentation] 二核ルテニウム錯体を用いた亜硝酸還元の理論的研究 (2018)
  • Author(s): 江木晃人，池田京，田中宏昌，塩田淑仁，有川康弘，吉澤一成
  • Organizer: 第１２回分子科学討論会2018福岡
• [Presentation] Synthetic Nitrite Reduction Cycle on a Dinuclear Ruthenium Complex Producing Ammonia (2018)
  • Author(s): Y. Arikawa, Y. Otsubo, H. Fujino, S. Horiuchi, E. Sakuda, K. Umakoshi
  • Organizer: 43rd International Conference on Coordination Chemistry (ICCC2018)
  • Int'l Joint Research
• [Presentation] Nitrite Reduction to Ammonia on a Dinuclear Ruthenium Complex (2018)
  • Author(s): Yasuhiro Arikawa, Yuji Otsubo, Hiroki Fujino, Shinnosuke Horiuchi, Eri Sakuda, Keisuke Umakoshi
  • Organizer: IRCCS-JST CREST Joint Symposium “Chemical sciences facing difficult challenges"
  • Int'l Joint Research
• [Presentation] Tp配位子を有する二核ルテニウム錯体上での亜硝酸イオン還元サイクルの研究 (2018)
  • Author(s): 中山智文、藤野大貴、有川康弘、堀内新之介、作田絵里、馬越啓介
  • Organizer: 日本化学会第98春季年会
• [Presentation] Formation of Ammonia by Reduction of Nitrito on a Dinuclear Ruthenium Complex (2017)
  • Author(s): 有川康弘、藤野大貴、大坪裕司、堀内新之介、作田絵里、馬越啓介
  • Organizer: 第64回有機金属化学討論会
• [Presentation] 二核ルテニウム錯体上での亜硝酸イオンからアンモニアへの還元 (2017)
  • Author(s): 藤野大貴、中山智文、大坪裕司、有川康弘、堀内新之介、作田絵里、馬越啓介
  • Organizer: 錯体化学第67回討論会
• [Remarks] 長崎大学大学院工学研究科 化学・物質工学コース 錯体化学研究室
  • URL: http://www.cms.nagasaki-u.ac.jp/lab/sakutai/