Syntheses and Reaction Chemistry of Reactive Silylene Transition-metal Complexes

• Project/Area Number: 19550056
• Research Category: Grant-in-Aid for Scientific Research (C)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Inorganic chemistry
• Research Institution: Tohoku University
• Principal Investigator: HASHIMOTO Hisako Tohoku University, 大学院・理学研究科, 准教授 (60291085)
• Project Period (FY): 2007 – 2008
• Project Status: Completed (Fiscal Year 2008)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2008: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2007: ¥2,730,000 (Direct Cost: ¥2,100,000、Indirect Cost: ¥630,000)
• Keywords: 有機金属錯体 / 高周期14族元素 / 遷移金属 / 反応化学 / ケイ素化学 / シリレン錯体 / ゲルミレン錯体 / ルテニウム / タングステン / 高周期元素 / ヘテロクムレン / アルキン / α,β-不飽和カルボニル化合物

Research Abstract

新しいタイプのシリレン錯体(金属-ケイ素二重結合化合物)の開発を行ない, このものが様々な不飽和有機化合物に対し, 従来に無い高い反応性を示すことを見出した. また, この化学をさらに高周期のゲルマニウムへ展開し, 類似の高い反応活性なゲルミレン錯体の開発を行なった。また, 未知の金属-ケイ素三重結合化合物の前駆体となり得るハロシリレン錯体の合成にも成功した。

Research Products

• [Journal Article] Reactions of a Hydrido(hydrosilylene)ruthenium Complex with Carbonyl Compounds (2009)
  • Author(s): Mitsuyoshi Ochiai, Hisako Hashimoto, Hiromi Tobita
  • Journal Title: Dalton Trans Pages: 1812-1814
  • Peer Reviewed
• [Journal Article] Reactions of a Hydrido(hydrosilylene)ruthenium Complex with Carbonyl Compounds (2009)
  • Author(s): M. Ochiai, et.al.
  • Journal Title: Dalton Trans Pages: 1812-1814
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of a Hydrido(hydrosilylene)ruthenium Complex and Its Reactions with Nitriles (2007)
  • Author(s): Mitsuyoshi Ochiai, Hisako Hashimoto, Hiromi Tobita
  • Journal Title: Angew. Chem. Int. Ed 46 Pages: 8192-8194
  • Peer Reviewed
• [Journal Article] Reactions of Hydrido(hydrosilylene)tungsten Complexes with α, β-Unsaturated Carbonyl Compounds : Selective Formation of (η^3-Siloxyallyl)tungsten Complexes (2007)
  • Author(s): Takahito Watanabe, Hisako Hashimoto, Hiromi Tobita
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 11338-11339
  • Peer Reviewed
• [Journal Article] Reactions of a Hydrido(hydrosilylene)tungsten Complex with Oxiranes (2007)
  • Author(s): Hisako Hashimoto, Mitsuyoshi Ochiai, Hiromi Tobita
  • Journal Title: J. Organomet. Chem. 692 Pages: 36-43
  • Peer Reviewed
• [Journal Article] Reactions, of a Hydrido(hydrosilylene)tungsten Complex with Oxiranes (2007)
  • Author(s): H. Hashimoto, et. al.
  • Journal Title: J. Organomet. Chem. 692 Pages: 36-43
  • Peer Reviewed
• [Journal Article] Reactions of Hydrido(hydrosilylene)tungsten Complexes with α,β-Unsaturated Carbonyl Compounds: Selective Formation of (η^3-Siloxyallyl)tungsten Complexes (2007)
  • Author(s): T. Watanabe, et. al.
  • Journal Title: J. Am. Chem. Soc. 129 Pages: 111338-11339
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of a Hydrido(hydrosilylene)ruthenium Complex and Its Reactions with Nitriles (2007)
  • Author(s): M. Ochiai, et. al.
  • Journal Title: Angew. Chem. Int. Ed. 46 Pages: 8192-8194
  • Peer Reviewed
• [Presentation] 水素架橋ビスシリレン)タングステン錯体とDMAPおよびアルコール類との反応 (2009)
  • Author(s): 橋本久子
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 西船橋
  • Year and Date: 2009-03-27
• [Presentation] 水素架橋ビス(シリレシ)タングステン錯体とDMAPおよびアルコール類との反応 (2009)
  • Author(s): 橋本久子
  • Organizer: 日本化学会第89回春季年会
  • Place of Presentation: 西船橋
  • Year and Date: 2009-03-27
• [Presentation] 多様な反応性を示す中性の末端型シリレン錯体 (2009)
  • Author(s): 橋本久子
  • Organizer: 学術創成研究・グローバルCOE(第五回有有機元素化学セミナー)
  • Place of Presentation: 京都
  • Year and Date: 2009-02-20
• [Presentation] 多様な反応性を示す中性の末端型シリレン錯体 (2009)
  • Author(s): 橋本久子
  • Organizer: 学術創成研究・グローバルCOE「第五回有機元素化学セミナー」
  • Place of Presentation: 京都
  • Year and Date: 2009-02-20
• [Presentation] Syntheses and Properties of Reactive Neutral Silylene Complexes of Tungsten and Ruthenium (2009)
  • Author(s): Hisako Hashimoto
  • Organizer: Joint Research Seminor Between York Univwersity and Tohoku University : Organometallic Chemistry Division
  • Place of Presentation: Sendai
  • Year and Date: 2009-01-20
• [Presentation] Syntheses and Properties of Reactive Neutral Silylene Complexes of Tungsten and Ruthenium (2009)
  • Author(s): H. Hashimoto
  • Organizer: Joint Research Seminar Between York Unive rsity and Tohoku University : Organometallic Chemistry Division
  • Place of Presentation: 仙台
  • Year and Date: 2009-01-20
• [Presentation] Experimental and Theoretical Studies on Bonding Nature and Dynamic Behavior of Tungsten Dihydrido Silyl Complexes (2008)
  • Author(s): Hisako Hashimoto
  • Organizer: The 2^<nd> International Symposium on Molecular Theory for Real System
  • Place of Presentation: Okazaki
  • Year and Date: 2008-10-04
• [Presentation] Reactivity of a Hydrido(hydrosilylene)ruthenium Complex toward Unsaturated Organic Molecules (2008)
  • Author(s): Hisako Hashimoto
  • Organizer: 第55回有機金属化学討論会
  • Place of Presentation: 大阪
  • Year and Date: 2008-09-28
• [Presentation] Experimental and Theoretical Studies on Bonding Nature and Dynamic Behavior of Tungsten Dihydrido Silyl Comnlxes (2008)
  • Author(s): H. Hashimoto
  • Organizer: The 2nd International Symposium on "Molecular Theory for Real System"
  • Place of Presentation: 岡崎
  • Year and Date: 2008-08-04
• [Presentation] 新しいタイプのシリレン遷移金属錯体の合成と性質 (2008)
  • Author(s): 橋本久子
  • Organizer: 第41回有機金属若手の会夏の学校
  • Place of Presentation: 須磨
  • Year and Date: 2008-07-07
• [Presentation] Neutral Silylene Complexes Having Functional Groups (2007)
  • Author(s): Hisako Hashimoto, Takahito Watanabe, Hiromi Tobita
  • Organizer: 2007 Workshop on Organometallic Chemistry(Grant-in Aid for Scientific Research on Priority Area "Synergy of Elements"
  • Place of Presentation: Wako
  • Year and Date: 2007-11-09
• [Presentation] Neutral Silylene Complexes Having Functional Groups (2007)
  • Author(s): 橋本久子
  • Organizer: 2007 Workshop on Organometallic Chemistry
  • Place of Presentation: 和光
  • Year and Date: 2007-11-09
• [Presentation] Syntheses, Structures, and Reactions of Transition-Metal Complexes (2007)
  • Author(s): Hisako Hashimoto
  • Organizer: Having Unsaturated Silicon-Based Legends The 1st Asian Symposium on Silicon
  • Place of Presentation: Zao
  • Year and Date: 2007-11-03
• [Presentation] Syntheses, Structures, and Reactions of Transition-Metal Complexes Having Unsaturated Silicon-Based Legends (2007)
  • Author(s): 橋本久子
  • Organizer: The 1st Asian Symposium on Silicon Chemistry
  • Place of Presentation: 蔵王
  • Year and Date: 2007-11-03
• [Presentation] Neutral Reactive Silylene Complexes (2007)
  • Author(s): Hisako Hashimoto
  • Organizer: Asian Science Forum (Chemistry)
  • Place of Presentation: Sendai
  • Year and Date: 2007-09-11
• [Presentation] Neutral Reactive Silylene Complexes (2007)
  • Author(s): 橋本久子
  • Organizer: Asian Science Forum (Chemistry)
  • Place of Presentation: 仙台
  • Year and Date: 2007-09-11
• [Presentation] Theoretical Investigation on an Interligand Interaction Observed in Hydrido(hydrosilylene)tungsten Complexes and Its Comparison with Ruthenium Analogue (2007)
  • Author(s): Hisako Hashimoto
  • Organizer: The 1st International Symposium on Molecular Theory for Real Systems
  • Place of Presentation: Kyoto
  • Year and Date: 2007-07-27
• [Presentation] Theoretical Investigation on an Interligand Interaction Observed in Hydrido(hydrosilylene)tungsten Complexes and Its Comparison with Ruthenium Analogue, (2007)
  • Author(s): 橋本久子
  • Organizer: The 1st International Symposium on Molecular Theory for Real Systems
  • Place of Presentation: 京都
  • Year and Date: 2007-07-27
• [Presentation] 反応活性な新しいタイプのシリレン錯体 (2007)
  • Author(s): 橋本久子
  • Organizer: 分子科学研究NKセミナー
  • Place of Presentation: 岡崎
  • Year and Date: 2007-07-19
• [Presentation] 官能基を持つシリレン遷移金属錯体の合成と反応化学 (2007)
  • Author(s): 橋本久子
  • Organizer: 第24回無機・分析化学コロキウム
  • Place of Presentation: 川渡, 宮城
  • Year and Date: 2007-06-02
• [Remarks]
  • URL: http://inorg.chem.tohoku.ac.jp/