Study on the transition metal complexes bearing a hypervalent silicon ligand and their application to catalytic reactions

• Project/Area Number: 25620024
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: The University of Tokyo
• Principal Investigator: Kano Naokazu 東京大学, 理学(系)研究科(研究院), 准教授 (00302810)
• Project Period (FY): 2013-04-01 – 2016-03-31
• Project Status: Completed (Fiscal Year 2015)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2015: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2014: ¥1,040,000 (Direct Cost: ¥800,000、Indirect Cost: ¥240,000); Fiscal Year 2013: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• Keywords: 14族元素 / 超原子価化合物 / 結合形成 / 高配位化合物 / スズ / 超原子価 / 結合 / ケイ素 / ゲルマニウム / 遷移金属

Outline of Final Research Achievements

Transition metal complexes bearing hypervalent silicon ligands were tried in vain to be synthesized for their application to efficient transition metal catalyst. The tin analogues were successfully synthesized. Their structures and properties were revealed. The tin ligand works as the Z-type ligand in these complexes. New types of homonuclear bonding of hypervalent germanium and tin atoms,respectively, were also synthesized and studied.

Research Products

• [Journal Article] Oxidative Bond Cleavage of the Silicon-Silicon Bond of a Pentacoordinated Disilicate (2015)
  • Author(s): N. Kano, H. Miyake. K. Sasaki, T. Kawashima
  • Journal Title: Heteroatom Chemistry Volume: 26 Pages: 183-186
  • Peer Reviewed
• [Journal Article] Interconversion among Dianionic, Anionic, and Neutral Compounds Bearing a Bond between Two Pentacoordinated Germanium Atoms (2015)
  • Author(s): N. Kano, S. Tsukada, Y. Shibata, T. Kawashima, H. Sato, J.-D. Guo, and S. Nagase
  • Journal Title: Organometallics Volume: 34 Issue: 1 Pages: 56-62
  • DOI: 10.1021/om500814g
  • Peer Reviewed / Open Access
• [Journal Article] Synthesis and Isolation of a Silylsilicate Containing Two Pentacoordinated Silicon Atoms by Monoprotonation of a Disilicate and Monodeprotonation of a Disilane (2014)
  • Author(s): N. Kano, K. Sasaki, H. Miyake, T. Kawashima
  • Journal Title: Organometallics Volume: 33 Issue: 9 Pages: 2358-2362
  • DOI: 10.1021/om500291k
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Interconversion of Dianionic, Anionic, and Neutral Compounds Bearing a Bond between Pentacoordinated Germanium Atoms (2016)
  • Author(s): Naokazu Kano, Satoru Tsukada, Yusuke Shibata, Takayuki Kawashima
  • Organizer: International Conference on the Coordination and Organometallic Chemistry of Germanium, Tin and Lead, 2016
  • Place of Presentation: Pardubice (Czech Republic)
  • Year and Date: 2016-08-28
  • Int'l Joint Research
• [Presentation] ５配位スズ配位子を有するアニオン性遷移金属錯体の合成、構造、電子状態 (2014)
  • Author(s): 狩野直和・柴田祐介・Havare, Nizam・宮地麻里子・小林康浩
  • Organizer: 錯体化学会第64回討論会
  • Place of Presentation: 中央大学（東京）
  • Year and Date: 2014-09-18 – 2014-09-20
• [Presentation] ５配位スズ配位子を有するアニオン性遷移金属錯体の合成と構造
  • Author(s): 狩野直和、柴田祐介、Havare, Nizam、宮地麻里子、小林康浩
  • Organizer: 日本化学会第94春季年会
  • Place of Presentation: 名古屋大学
• [Presentation] Properties of Tin-Iron Bond of the Anionic Iron Complex Bearing a Pentacoordinated Tin Ligand
  • Author(s): Naokazu Kano, Yusuke Shibata, Nizam Havare, Mariko Miyachi, Yasuhiro Kobayashi
  • Organizer: International Symposium on Coordination Programming (ISCP-2014)
  • Place of Presentation: The University of Tokyo
• [Book] 現代ケイ素化学：体系的な基礎概念と応用に向けて (2013)
  • Author(s): 狩野直和，川島隆幸
  • Total Pages: 39
  • Publisher: 化学同人