Chemistry of σ Electron Systems Based on Inverted σ-bonded Compounds

• Project/Area Number: 20685004
• Research Category: Grant-in-Aid for Young Scientists (A)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Tohoku University
• Principal Investigator: IWAMOTO Takeaki 東北大学, 大学院・理学研究科, 教授 (70302081)
• Project Period (FY): 2008 – 2011
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥25,350,000 (Direct Cost: ¥19,500,000、Indirect Cost: ¥5,850,000); Fiscal Year 2011: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2010: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2009: ¥4,290,000 (Direct Cost: ¥3,300,000、Indirect Cost: ¥990,000); Fiscal Year 2008: ¥12,480,000 (Direct Cost: ¥9,600,000、Indirect Cost: ¥2,880,000)
• Keywords: 反転σ結合 / ケイ素 / ビシクロ[1.1.1]ペンタシラン / かご型化合物 / X 線結晶構 造解析 / X線結晶構造解析 / スタファン / σ共役 / 多環式シラン / ペルシラスタファン / σ－π共役 / σ電子系 / 高周期14族元素 / 合成 / 物性 / 溶媒分離イオン対 / カルボメタレーション / シリルアニオン

Research Abstract

We focused on "inverted σ bonds" that show unusual geometry and electronic properties and we synthesize several heavier group-14 element compounds bearing the inverted σ bonded compounds as their components. We have successfully prepared a series of functionalized bicyclo[1.1.1]pentasilanes that are one of the smallest molecular silicon cluster. Using the bicyclopentasilane units we successfully synthesized a series of persila[n]staffanes and revealed remarkable conjugation between the silicon cages. We also synthesized a dimer of 1,3-disila- bicyclo[1.1.0]butane which has an inverted Si-Si σ bond between the bridgehead silicon atoms. UV-vis spectrum and DFT calculations of the dimer show that significant interactions exist between the bridgehead Si-Si bond in the disilabicyclobutane units.

Research Products

• [Journal Article] Persilastaffanes: Design, Synthesis, Structure, and Conjugation between Silicon Cages (2012)
  • Author(s): T. Iwamoto, D. Tsushima, E. Kwon, S. Ishida, H. Isobe
  • Journal Title: Angew. Chem. Int. Ed. Volume: 51 Issue: 10 Pages: 2340-2344
  • DOI: 10.1002/anie.201106422
  • Peer Reviewed
• [Presentation] 橋頭位にアリール基を持つ新規ビシクロ[1.1.1]ペンタシランの合成と性質 (2013)
  • Author(s): 津島大輔、石田真太郎、岩本武明
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 草津
  • Year and Date: 2013-03-25
• [Presentation] Persila[n]staffanes and Related Polycyclic Oligosilanes (2012)
  • Author(s): Takeaki Iwamoto
  • Organizer: 4th Asian Silicon Symposium
  • Place of Presentation: Tsukuba
  • Year and Date: 2012-10-22
• [Presentation] Synthesis and Structure of Persilastaffanes and Related Silicon Compounds (2012)
  • Author(s): Takeaki Iwamoto
  • Organizer: 243^<rd> ACS National Meeting & Exposition(招待講演)
  • Place of Presentation: San Diego, USA
  • Year and Date: 2012-03-26
• [Presentation] [n]スタファンケイ素類縁体の合成とかご型ケイ素骨格間の共役 (2012)
  • Author(s): 津島大輔、石田真太郎、權垠相、磯部寛之、岩本武明
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 横浜
  • Year and Date: 2012-03-25
• [Presentation] Synthesis and Structure of Persilastaffanes and Related Silicon Compounds (2012)
  • Author(s): Takeaki Iwamoto
  • Organizer: 243rd ACS National Meeting & Exposition
  • Place of Presentation: San Diego, USA
  • Invited
• [Presentation] 反転σ結合を有するケイ素クラスターの合成と構造 (2011)
  • Author(s): 降矢裕一、石田真太郎、大野公一、岩本武明
  • Organizer: 平成23年度化学系学協会東北大会
  • Place of Presentation: 仙台
  • Year and Date: 2011-09-17
• [Presentation] [2]スタファンケイ素類縁体の合成と構造 (2011)
  • Author(s): 津島大輔、石田真太郎、磯部寛之、岩本武明
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学横浜キャンパス
  • Year and Date: 2011-03-26
• [Presentation] [2]スタファンケイ素類縁体の合成と構造 (2011)
  • Author(s): 津島大輔・石田真太郎・磯部寛之・岩本武明
  • Organizer: 日本化学会第91春季年会
  • Place of Presentation: 神奈川大学
  • Year and Date: 2011-03-26
• [Presentation] [n]スタファンケイ素類縁体の合成、構造、および電子状態 (2011)
  • Author(s): 津島大輔、石田真太郎、權垠相、磯部寛之、岩本武明
  • Organizer: 第22回基礎有機化学討論会
  • Place of Presentation: 筑波
• [Presentation] Reactions of long bond isomers of 1, 3-dimetallabicyclo[1.1.0]butanes (2010)
  • Author(s): Daisuke Tsushima, Shintaro Ishida, Hiroyuki Isobe, Takeaki Iwamoto
  • Organizer: Pacifichem 2010
  • Place of Presentation: ハワイ、米国(依頼講演)
  • Year and Date: 2010-12-16
• [Presentation] Synthesis, structure, and reactions of novel silicon analogs of bicyclo[1.1.1]pentanes (2010)
  • Author(s): 津島大輔、石田真太郎、磯部寛之、 岩本武明
  • Organizer: 環太平洋国際化学会議2010
  • Place of Presentation: ホノルル、米国
  • Year and Date: 2010-12-15
• [Presentation] 新規ビシクロ[1.1.1]ペンタシランの合成と官能基化 (2010)
  • Author(s): 津島大輔、石田真太郎、岩本武明
  • Organizer: 第14回ケイ素化学協会シンポジウム
  • Place of Presentation: ニューウェルシティ湯河原
  • Year and Date: 2010-11-19
• [Presentation] Synthesis, Structure and Reactions of Novel Silicon Analogs of Bicyclo[1.1.1]pentasilanes (2010)
  • Author(s): 津島大輔、石田真太郎、磯部寛之、岩本武明
  • Organizer: Tohoku University Global Center of Excellence Program Summer School 2010
  • Place of Presentation: 東北大学
  • Year and Date: 2010-08-19
• [Presentation] Silicon Compounds with an Inverted Sigma Bond, G-COE Dalian University of Technology . (2009)
  • Author(s): Takeaki Iwamoto
  • Organizer: Tohoku University Joint Symposium
  • Place of Presentation: 東北大学萩ホール(依頼講演)
  • Year and Date: 2009-12-09
• [Presentation] 新規ビシクロ[1.1.1]ペンタシランの合成と反応 (2009)
  • Author(s): 岩本武明・津島大輔・磯部寛之
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学今出川キャンパス
  • Year and Date: 2009-09-09
• [Presentation] 新規ビシクロ[1.1.1]ペンタシランの合成と構造 (2009)
  • Author(s): 津島大輔、岩本武明、磯部寛之
  • Organizer: 第89日本化学会春季年会
  • Place of Presentation: 日本大学理工学部
  • Year and Date: 2009-03-27
• [Remarks] (1)Angewandte Chemie誌のFrontispiece、プレスリリース(2011年、No.50)、Chemistry Viewsに取り上げられた。(雑誌論文(1)に関して)
  • URL: http://onlinelibrary.wiley.com/journal/10.1002/(ISSN)1521-3773/homepage/press/201150press.htm