ヘキサシアノトリキナレンメタンジアニオンの構造およびその酸化体の性質

• 池田 淳哉

• 松本 幸三

• 川瀬 毅

• 小田 雅司

書誌事項

タイトル別名

• Structure of Hexacyanotriquinarenemethane Dianion and Properties of Its Oxidized Species

抄録

We recently reported the synthesis and physicochemical properties of sodium salt of hexacyanotriquinarenemethane (HCTQM) dianion 1a which has a tetrapolar structure. After examination of various counter cations, we succeeded in obtaining a single crystal of pyridinium salt of HCTQM dianion 1b suitable for X-ray analysis. Now we report the molecular and crystal structure of 1b as well as the oxidation of 1a directed to the detection of HCTQM diradical 2. The proton bound to the nitrogen in pyridinium ring forms a hydrogen bond with the cyano group of the neighboring HCTQM dianion. The distance between the nitrogen atoms participating in the hydrogen bond is 2.80 angstrom and the angle of N-H-N is 159.5°. Three quinarene moieties are twisted each other and form a propeller structure. HCTQM dianion face each other in head-to-tail manner and two cyano groups directing outside participate in the hydrogen bond with pyridinium.The oxidation of 1a with copper (II) chloride gave the cyclic dimer of diradical 2. In order to detect diradical 2, the solution of 1a in DMF or butyronitrile was oxidized electolytically at -100 °C. But the ESR signal assignable to 2 wasn't obtained although the signal due to a radical species was observed.

収録刊行物

• 基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集）

  基礎有機化学討論会要旨集（基礎有機化学連合討論会予稿集） 16 (0), 1064-1064, 2002

  基礎有機化学会（基礎有機化学連合討論会）

キーワード

• Trimethylenemethane
• Hexacyanotriquinarenemethane
• Molecular structure
• Oxidation
• Extended trimethylenemethane diradical

詳細情報

• CRID: 1390001205554804608
• NII論文ID: 130004644603
• DOI: 10.11494/kisoyuki.16.0.1064.0
• データソース種別:
  • JaLC
  • CiNii Articles
• 抄録ライセンスフラグ: 使用不可