Development and application of reversible addition reaction of endohedral metallofullerenes

2008 Fiscal Year Final Research Report

• Project/Area Number: 19750027
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Tokyo Gakugei University
• Principal Investigator: MAEDA Yutaka Tokyo Gakugei University, 教育学部, 准教授 (10345324)
• Co-Investigator(Renkei-kenkyūsha): AKASAKA Takeshi 筑波大学, 先端学際領域研究センター, 教授 (60089810)
• Project Period (FY): 2007 – 2008
• Keywords: フラーレン / 金属内包フラーレン / 可逆付加反応 / 付加反応

Research Abstract

金属内包フラーレンおよびフラーレンに対し、ジエン、カルベン、ラジカル種等を用いた化学反応を検討したところ、種々の対応する付加体の合成に成功した。付加体のキャラクタリゼーションを行い、新規誘導体の構造と特性の評価を試みた。ジエンを鍵とする、金属内包フラーレンの可逆付加反応系の構築を目的とし、研究を推進したところ、1)高い位置選択性で付加反応が進行すること、2)化学反応性を用いるジエンの置換基にて制御し得ること、3)結晶構造解析にて構造を決定し、フラーレンケージの歪みおよび電荷密度が高選択的付加反応の因子であること、4)結晶中において、付加体のスピン密度によってはダイマー構造をとること、を明らかにした。さらに、世界に先駆けて異なる2つの官能基を高い位置選択性で金属内包フラーレンに導入することに成功し、金属内包フラーレンを核とする三分子系機能性分子の構築に向けたモデルを提案することができた。

Research Products

• [Journal Article] Radical Coupling Reaction of Parama gnetic Endohedral Metallofullerene La@C82 (2008)
  • Author(s): Y. Takano, A. Yomogida, H. N ikawa, M. Yamada, T. Wakahara, T. T suchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, T. Kato, Z. Slanina, N. Mizorogi, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 16224-16230
• [Journal Article] Does Gd@C82 Have an Anomalous Endohe dral Structure? Synthesis and Singl e Crystal X-ray Structure of the Ca rbene Adduct (2008)
  • Author(s): T. Akasaka, T. Kono, Y. Takematsu, H. Nikawa, T. Nakahod o, T. Wakahara, M. O. Ishitsuka, T. Tsuchiya, Y. Maeda, M. T. H. Liu, K. Yoza, T. Kato, K. Yamamoto, N. M izorogi, Z. Slanina, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 12840-12841
• [Journal Article] Chemical Understanding of a Non-IPR Metallofullerene: Stabilization of Encaged Metals on Fused-pentagon B onds in La2@C72 (2008)
  • Author(s): X. Lu, H. Nikawa, T. Nakahodo, T. Tsuchiya, M. O. Ishit suka, Y. Maeda, T. Akasaka, M. Toki, H. Sawa, Z. Slanina, N. Mizorogi, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 9129-9136
• [Journal Article] Metal Atoms Collinear with the Spir o Carbon of 6,6-Open Adducts, M2@C80 (Ad) (M = La and Ce, Ad = Adamantyl idene) (2008)
  • Author(s): M. Yamada, C. Someya, T. Wa kahara, T. Tsuchiya, Y. Maeda, T. A kasaka, K. Yoza, E. Horn, M. T. H. Liu, N. Mizorogi, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 1171-1176
• [Journal Article] Addition of Adamantylidene to La2@C 78: Isolation and Single-Crystal Xray Structural Determination of the Monoadducts (2008)
  • Author(s): B. Cao, H. Nikawa, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, H. Sawa, Z. Slanina, N. M izorogi, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 983-989
• [Journal Article] Nanorods of Endohedral Metallofulle rene Derivative (2008)
  • Author(s): T. Tsuchiya, R. Ku mashiro, K. Tanigaki, Y. Matsunaga, M. O. Ishitsuka, T. Wakahara, Y. M aeda, Y. Takano, M. Aoyagi, T. Akas aka, M. T. H. Liu, T. Kato, K. Suen aga, J. S. Jeong, S. Iijima, F. Kim ura, T. Kimura, S. Nagase
  • Journal Title: J. Am. Chem. Soc. 130 Pages: 450-451
• [Journal Article] Bis-carbene Adducts of Non-IPR La2@ C72: Localization of High Reactivity around Fused-pentagons and Toward Controllable Tuning of Electrochemi cal Properties of Metallofullerenes (2008)
  • Author(s): X. Lu, H. Nikawa, T. Tsuchiya, Y. Maeda, M. O. Ishitsuka, T. Akasaka, M. Toki, H. Sawa, Z. Slanina, N. M izorogi, S. Nagase
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 8642-8645
• [Journal Article] Observation of 13C NMR Chemical Shifts of Metal Carbides Encapsulated in Fullerenes: Sc2C2@C82, Sc2C2@C84, and Sc3C2@C80 (2008)
  • Author(s): Y. Yamazaki, K. Nakajima, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, M. Waelchili, N. Mizorogi, S. Nagase
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 7905-7908
• [Journal Article] [2+1]-Cycloaddition of Nitrene onto C60 Revisited: Interconversion between Aziridinofullerene and Azafulleroid (2008)
  • Author(s): T. Nakahodo, M. Okada, H. Morita, T. Yoshimura, M. O. Ishitsuka, T. Tsuchiya, Y. Maeda, H. Fujihara, T. Akasaka, X. Gao, S. Nagase
  • Journal Title: Angew. Chem. Int. Ed. 47 Pages: 1298-1300
• [Journal Article] Location of the Metal Atoms in Ce2@C78 and its Bis-silylated Derivative (2008)
  • Author(s): M. Yamada, T. Wakahara, T. Tsuchiya, Y. Maeda, M. Kako, T. Akasaka, K. Yoza, E. Horn, N. Mizorogi, S. Nagase
  • Journal Title: Chem. Commun. Pages: 558-560
• [Journal Article] Spectroscopic and Theoretical Study of Endohedral Dimetallofullerene Having a Non-IPR Fullerene Cage: Ce2@C72 (2008)
  • Author(s): M. Yamada, T. Wakahara, T. Tsuchiya, Y. Maeda, T. Akasaka, N. Mizorogi, S. Nagase
  • Journal Title: J. Phys. Chem. A 112 Pages: 7627-7631
• [Journal Article] Isolation and Characterization of Carbene Derivatives of La@C82(Cs) (2008)
  • Author(s): T. Akasaka, T. Kono, Y. Matsunaga, T. Wakahara, T. Nakahodo, M. O. Ishitsuka, Y. Maeda, T. Tsuchiya, T. Kato, M. T. H. Liu, N. Mizorogi, Z. Slanina, S. Nagase
  • Journal Title: J. Phys. Chem. A 112 Pages: 1294-1297
• [Journal Article] Synthesis of Selenylfullerene with Selenium-containing Dibenzo[b, g]cyclooctane Moiety (2008)
  • Author(s): T. Nakahodo, K. Takahashi, M. O. Ishitsuka, T. Tsuchiya, Y. Maeda, H. Fujihara, S. Nagase, T. Akasaka
  • Journal Title: Tetrahedron Lett. 49 Pages: 2302-2305
• [Journal Article] Experimental and Theoretical Studie s of the Scandium Carbide Endohedral Metallofullerene Sc2C2@C82 and Its Carbene Derivative (2007)
  • Author(s): Y. Iiduka, T. Wakahara, K. Nakajima, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, K. Yoza, M. T. H. Liu, N. Mizorogi, S. Nagase
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 5562-5564
• [Journal Article] Two-dimensional Hopping Motion of Encapsulated La Atoms in Silylated La2@C80 (2007)
  • Author(s): T. Wakahara, M. Yamada, S. Takahashi, T. Nakahodo, T. Tsuchiya, Y. Maeda, T. Akasaka, M. Kako, K. Yoza, E. Horn, N. Mizorogi, S. Nagase
  • Journal Title: Chem. Commun. Pages: 2680-2682
• [Presentation] 2 つの異なる置換基によるLa@C82の化学修飾のおける位置選択性 (2009)
  • Author(s): 佐藤 悟・前田 優・稲田 浩二・山田 道夫・土屋敬広・石塚 みどり・長谷川 正・赤阪 健・加藤 立久・溝呂木 直美・Zdenek, Slanina・永瀬 茂
  • Organizer: 日本化学会第89 回春季年会
  • Place of Presentation: 船橋
  • Year and Date: 20090327-30
• [Presentation] 常磁性金属内包フラーレンLa@C82 におけるラジカルカップリング反応 (2009)
  • Author(s): 高野 勇太・蓬田 知行・二川 秀史・若原 孝次・土屋 敬広・石塚 みどり・前田 優・赤阪 健・加藤 立久・スラニナ ズデネク・溝呂木 直美・永瀬 茂
  • Organizer: 日本化学会第89 回春季年会
  • Place of Presentation: 船橋
  • Year and Date: 20090327-30
• [Presentation] Synthesis and Characterization of Sc@C82 Derivatives (2009)
  • Author(s): M. Hachiya, Y. Yamazaki, M. O. Ishitusuka, T. Tsuchiya, Y. Maeda, T. Akasaka, N. Mizorogi, S. Nagase
  • Organizer: プレ戦略イニシアティブ「機能分子創成研究拠点」シンポジウム
  • Place of Presentation: つくば
  • Year and Date: 20090316-17
• [Presentation] Unconventional Bingel adducts of the open-shell metallofullerene La@C82 (2009)
  • Author(s): L. Feng, T. Tsuchiya, T. Wakahara, T. Nakahodo, Q. Piao, Y. Maeda, T. Akasaka, T. Kato, K. Yoza, E. Horn, N. Mizorogi, S. Nagase
  • Organizer: プレ戦略イニシアティブ「機能分子創成研究拠点」シンポジウム
  • Place of Presentation: つくば
  • Year and Date: 20090316-17
• [Presentation] Reversible Addition Reaction of Endohedral Metallofullerene La@C82 (2009)
  • Author(s): S. Sato, Y. Maeda, K. Inada, H. Nikawa, M. Yamada, N. Mizorogi, T. Hasegawa, T. Tsuchiya, T. Akasaka, T. Kato, Z. Slanina, S. Nagase
  • Organizer: プレ戦略イニシアティブ「機能分子創成研究拠点」シンポジウム
  • Place of Presentation: つくば
  • Year and Date: 20090316-17
• [Presentation] Radical Coupling Reaction of Parama gnetic Endohedral Metallofullerene La@C82 (2009)
  • Author(s): Y. Takano, A. Yomogida, H. Nikawa, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, T. Kato, Z. Slanina, N. Mizorogi, S. Nagase
  • Organizer: The 2nd International Symposium on Interdisciplinary Material Science (ISIMS-2009)
  • Place of Presentation: Tsukuba, Japan
  • Year and Date: 20090309-10
• [Presentation] Reversible Addition Reaction of Endohedral Metallofullerene La@C82 (2009)
  • Author(s): S. Sato, Y. Maeda, K. Inada, H. Nikawa, M. Yamada, N. Mizorogi, T. Hasegawa, T. Tsuchiya, T. Akasaka, T. Kato, Z. Slanina, S. Nagase
  • Organizer: he 2nd International Symposium on Interdisciplinary Material Science (ISIMS-2009)
  • Place of Presentation: Tsukuba, Japan
  • Year and Date: 20090309-10
• [Presentation] Reversible Addition Reaction of Endohedral Metallofullerene La@C82 (2008)
  • Author(s): S. Sato, Y. Maeda, K. Inada, M. Yamada, T. Tsuchiya, M. O. Ishitsuka, T. Hasegawa, T. Akasaka, T. Kato, N. Mizorogi, S. Nagase
  • Organizer: PRiME 2008 (Pacific Rim Meeting, 214th ECS Meeting)
  • Place of Presentation: Honolulu, USA.
  • Year and Date: 20081012-17
• [Presentation] 常磁性金属内包フラーレンLa@C82 におけるラジカルカップリング反応 (2008)
  • Author(s): 高野勇太・蓬田知行・二川秀史・若原孝次・土屋敬広・生沼みどり・前田 優・赤阪 健・加藤立久・Zdenek Slanina・溝呂木 直美・永瀬 茂
  • Organizer: 第19 回基礎有機化学討論会
  • Place of Presentation: 吹田市
  • Year and Date: 20081003-05
• [Presentation] 金属内包フラーレンLa@C82 の可逆反応 (2008)
  • Author(s): 佐藤 悟・前田 優・稲田浩司・山田道夫・土屋敬広・生沼みどり・長谷川 正・赤阪 健・加藤立久・溝呂木直美・Zdenek Slanina・永瀬 茂
  • Organizer: 第19 回基礎有機化学討論会
  • Place of Presentation: 吹田市
  • Year and Date: 20081003-05
• [Presentation] Sc@C82 とその誘導体の合成と物性解明 (2008)
  • Author(s): 蜂屋 誠・山崎裕子・土屋敬広・前田 優・赤阪 健・溝呂木直美・永瀬 茂
  • Organizer: 第2回日本化学会関東支部大会、桐生市
  • Place of Presentation: 桐生市
  • Year and Date: 20080918-19
• [Presentation] Radical Coupling Reaction of Paramagnetic Endohedral Metallofullerene La@C82 (2008)
  • Author(s): Y. Takano, A. Yomogida, H. Nikawa, T. Wakahara, T. Tsuchiya, M. O. Ishitsuka, Y. Maeda, T. Akasaka, T. Kato, Z. Slanina, N. Mizorogi, S. Nagase
  • Organizer: 第35 回記念フラーレン・ナノチューブ総合シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 20080827-29
• [Presentation] Bis-carbene Derivatives of a Non-IPR Metallofullerene: La2@C72 (2008)
  • Author(s): X. Lu, H. Nikawa, M. O. Ishitsuka, T. Tsuchiya, Y. Maeda, T. Akasaka, Z. Slanina, N. Mizorogi, S. Nagase
  • Organizer: 第35 回記念フラーレン・ナノチューブ総合シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 20080827-29
• [Presentation] Reversible and Regioselective Reaction of La@C82 with 1,2,3,4,5-Pentamethylcyclopentadiene (2008)
  • Author(s): S. Sato, Y. Maeda, K. Inada, M. Yamada, T. Tsuchiya, M. O. Ishitsuka, T. Hasegawa, T. Akasaka, T. Kato, N. Mizorogi, Z. Slanina, S. Nagase
  • Organizer: 第35 回記念フラーレン・ナノチューブ総合シンポジウム
  • Place of Presentation: 東京
  • Year and Date: 20080827-29
• [Presentation] Positional Control of Encapsulated Atoms Inside a Fullerene Cage by Exohedral Chemical Functionalization (2008)
  • Author(s): M. Yamada, C. Someya, T. Wakahara, T. Tsuchiya, T. Akasaka, Y. Maeda, K. Yoza, N. Mizorogi, S. Nagase
  • Organizer: 213th ECS Meeting
  • Place of Presentation: Phoenix, USA
  • Year and Date: 20080518-22
• [Presentation] 金属内包フラーレンLa@C82 の可逆付加反応 (2008)
  • Author(s): 佐藤 悟・前田 優・稲田浩司・山田道夫・土屋敬広・生沼みどり・長谷川 正・赤阪 健・加藤立久・溝呂木直美・永瀬 茂
  • Organizer: 第2回日本化学会関東支部大会
  • Place of Presentation: 桐生市
  • Year and Date: 20080318-19
• [Presentation] La@C82 とシクロペンタジエン誘導体の反応 (2008)
  • Author(s): 佐藤悟・前田優・稲田浩司・長谷川正・山田道夫・土屋敬広・赤阪健・加藤立久・溝呂木直美・永瀬茂
  • Organizer: 第34 回フラーレン・ナノチューブ総合シンポジウム
  • Place of Presentation: 名古屋
  • Year and Date: 20080300
• [Presentation] Diels-Alder Reaction of Endohedral Metallofullerene La@C82 (2008)
  • Author(s): 佐藤悟・前田優・稲田浩司・山田道夫・土屋敬広・長谷川正・赤阪健・加藤立久・溝呂木直美・永瀬茂
  • Organizer: 日本化学会第88 春季年会
  • Place of Presentation: 池袋
  • Year and Date: 20080300
• [Presentation] La@C82 とシクロペンタジエン誘導体の可逆反応 (2007)
  • Author(s): 佐藤悟・前田優・稲田浩司・長谷川正・山田道夫・土屋敬広・赤阪健・加藤立久・溝呂木直美・永瀬茂
  • Organizer: 第18 回日本化学会関東支部茨城地区研究交流会
  • Place of Presentation: 水戸
  • Year and Date: 20071100
• [Presentation] La@C82 とシクロペンタジエン誘導体の可逆反応 (2007)
  • Author(s): 佐藤悟・前田優・稲田浩司・長谷川正・山田道夫・土屋敬広・赤阪健・加藤立久・溝呂木直美・永瀬茂
  • Organizer: 日本化学会第1回関東支部大会
  • Place of Presentation: 八王子
  • Year and Date: 20070900
• [Presentation] La@C82 とシクロペンタジエン誘導体の可逆付加反応 (2007)
  • Author(s): 佐藤悟・前田優・稲田浩司・長谷川正・山田道夫・土屋敬広・赤阪健・加藤立久・溝呂木直美・永瀬茂
  • Organizer: 第57 回有機反応化学討論会
  • Place of Presentation: 東広島
  • Year and Date: 20070900
• [Presentation] La@C82 とシクロペンタジエン誘導体の可逆反応 (2007)
  • Author(s): 佐藤悟・前田優・稲田浩司・長谷川正・山田道夫・土屋敬広・赤阪健・加藤立久・溝呂木直美・永瀬茂
  • Organizer: 第33 回フラーレン・ナノチューブ総合シンポ ジウム
  • Place of Presentation: 福岡
  • Year and Date: 20070700
• [Presentation] Regioselective reaction of La@C82 (2007)
  • Author(s): Yutaka Maeda, Tadashi Hasegawa, Takahiro Tsuchiya, TakatsuguWakahara, Takeshi Akasaka, Tatsuhisa Kato,Shigeru Nagase
  • Organizer: ISNA12th
  • Place of Presentation: 淡路
  • Year and Date: 20070700