Development of separation method of enantiomer of polyoxometalate and application as chiral catalysts

• Project/Area Number: 26420787
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Multi-year Fund
• Section: 一般
• Research Field: Catalyst/Resource chemical process
• Research Institution: Hiroshima University
• Principal Investigator: Sadakane Masahiro 広島大学, 工学研究院, 准教授 (10342792)
• Project Period (FY): 2014-04-01 – 2017-03-31
• Project Status: Completed (Fiscal Year 2016)
• Budget Amount: ¥5,070,000 (Direct Cost: ¥3,900,000、Indirect Cost: ¥1,170,000); Fiscal Year 2016: ¥910,000 (Direct Cost: ¥700,000、Indirect Cost: ¥210,000); Fiscal Year 2015: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2014: ¥2,990,000 (Direct Cost: ¥2,300,000、Indirect Cost: ¥690,000)
• Keywords: ポリオキソメタレート / キラル / ルテニウム / 触媒 / エナンチオマー / 異性化

Outline of Final Research Achievements

We found a new phenomena that there is an equilibrium between alpha1 and alpha2 isomer of mono-lacunary Dawson-type phosphotungstate, [P2W17O61]10-, in lithium acetate buffer (pH ca. 5). By utilizing this phenomena, we are able to synthesize alpha1-isomer of mono-transition metal substituted Dawson-type phospotungstate, [alpha1-P2W17O61M]7- (M = Ru, Zn, Mn, Co) from the alpha2-isomer of the mono-lacunary Dawson-type phosphotungstate, [alpha2-P2W17O61]10-. The alpha1-isomer of mono-transition metal substituted Dawson-type phospotungstate, [alpha1-P2W17O61M]7- (M = Ru, Zn, Mn, Co) is a chiral compound and have potential as chiral materials.

Research Products

• [Int'l Joint Research] Department de Quimica Fisica/i Inorganica/Universitat Rovira i Virgili(スペイン)
• [Int'l Joint Research] Department of Chemistry/University of Delhi(インド)
• [Int'l Joint Research] Departament de Quimica Fisica/i Inorganica/Universitat Rovira i Virgili(スペイン)
• [Int'l Joint Research] Laboratoire de Chimie-Physique/Universite Paris-Sud(フランス)
• [Journal Article] Synthesis of epsilon-Keggin-Type Cobaltomolybdate-Based 3D Framework Material and Characterization Using Atomic-Scale HAADF-STEM and XANES (2017)
  • Author(s): Igarashi, T; Zhang, ZX; Haioka, T; Iseki, N; Hiyoshi, N; Sakaguchi, N; Kato, C; Nishihara, S; Inoue, K; Yamamoto, A; Yoshida, H; Tsunoji, N; Ueda, W; Sano, T; Sadakane, M
  • Journal Title: INORGANIC CHEMISTRY Volume: 56 Issue: 4 Pages: 2042-2049
  • DOI: 10.1021/acs.inorgchem.6b02748
  • Peer Reviewed / Open Access / Int'l Joint Research
• [Journal Article] Lanthanoid template isolation of alpha-(1,5) isomer of di-Cobalt (II) substituted Keggin type phosphotungstates: Syntheses, characterization and magnetic properties (2016)
  • Author(s): R. Gupta, F. Hussain, M. Sadakane, C. Kato, K. Inoue, S. Nishihara
  • Journal Title: Inorg. Chem. Volume: 55 Issue: 17 Pages: 8292-8300
  • DOI: 10.1021/acs.inorgchem.5b02772
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Preparation of alpha1- and alpha2-isomers of Mono-Ru-substituted Dawson-type Phosphotungstates with an Aqua Ligand and comparison of their Redox Potentials, Catalytic Activities, and Thermal stabilities with Keggin-type derivatives (2016)
  • Author(s): Kensuke Nishiki, Naoya Umehara, Yusuke Kadota, Xavier Lopez, Josep M. Poblet, Charyle Ayingone Mezui, Anne-Lucie Teillout, Israel M. Mbomekalle, Pedro de Oliveira, Mayumi Miyamoto, Tsuneji Sano, and Masahiro Sadakane
  • Journal Title: Dalton Transactions Volume: 45 Issue: 9 Pages: 3715-3726
  • DOI: 10.1039/c5dt04219d
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] Preparation and structural characterization of mono-Ru-substituted alpha2-Dawson-type phosphotungstate with a carbonyl ligand and other Ru(CO)-substiuted heteropolytungstates (2015)
  • Author(s): Kensuke Nishiki, Shuhei Ogo, Hiromichi Ohta, Tsuneji Sano, Masahiro Sadakane
  • Journal Title: European Journal of Inorganic Chemistry Volume: 2015 Issue: 16 Pages: 2714-2723
  • DOI: 10.1002/ejic.201500226
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] 単欠損Dawson型リンタングステートの異性化の検討と金属単置換alpha1-Dawson型リンタングステートの合成 (2016)
  • Author(s): 山根康平、佐野庸治、定金正洋、津野地直
  • Organizer: 錯体化学会 第66回討論会
  • Place of Presentation: 福岡大学 七隈キャンパス
  • Year and Date: 2016-09-12
• [Presentation] 単欠損Dawson型リンタングステートの異性化の検討と金属単置換α1-Dawson化合物の合成 (2016)
  • Author(s): 山根 康平・定金 正洋・佐野 庸治・津野地 直
  • Organizer: 日本化学会第96回春年会
  • Place of Presentation: 同志社大学、京田辺市
  • Year and Date: 2016-03-25
• [Presentation] 単欠損 Dawson 型リンタングステートの異性化の検 討とルテニウム単置換 a1-Dawson 化合物の合成 (2015)
  • Author(s): 山根 康平・定金 正洋・佐野 庸治・津野地 直
  • Organizer: 錯体討論会第65回討論会
  • Place of Presentation: 奈良女子大学、奈良市
  • Year and Date: 2015-09-21