"One-Electron Sigma Bond" - A Challenge to a New Theory of the Chemical Bond Developed by Using Radical Cations

2014 Fiscal Year Final Research Report

• Project/Area Number: 24655037
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Osaka Prefecture University
• Principal Investigator: IKEDA Hiroshi 大阪府立大学, 工学(系)研究科(研究院), 教授 (30211717)
• Research Collaborator: YAMAMOTO Yosuke 広島大学, 大学院理学研究科, 教授 (50158317) ; OHTA Eisuke 大阪府立大学, 大学院工学研究科, 助教 (20550320) ; MATSUI Yasunori 大阪府立大学, 大学院工学研究科, 博士研究員 ; KURAMOTO Yutaro 大阪府立大学, 大学院工学研究科
• Project Period (FY): 2012-04-01 – 2015-03-31
• Keywords: 有機化学 / 電子移動反応 / 光化学反応 / レーザーフラッシュフォトリシス / 熱ルミネッセンス / 過渡吸収 / ラジカルカチオン塩 / DFT計算

Outline of Final Research Achievements

In this work, to prove the one-electron σ bond experimentally, electron-transfer reactions of cage compounds 1 were examined under various conditions.
In laser flash photolysis of 1b having tolyl groups, under photoinduced electron-transfer conditions, an absorption spectrum of the radical cation intermediate having a one-electron σ bond 1b･+ was observed successfully, as expected.
On the other hand, it was expected that 1d･+SbCl6-, a salt of a stable radical cation 1d･+ having a one-electron σ bond, would be produced in an electron-transfer reaction of 1d having the triphenylamine moiety by using aminium salt (4-BrC6H4)3N･+SbCl6- as a one-electron oxidant. In fact, however, a phenolate-ion containing salt 5d-Cl+SbCl6-, which is totally different from 1d･+SbCl6-, was unexpectedly produced in a high yield.

Free Research Field

有機化学