Syntheses and Reaction Chemistry of New Transition Metal Complexes Having Metal-Heavier Group 14 Element Multiple Bonds

2011 Fiscal Year Final Research Report

• Project/Area Number: 21550054
• 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 東北大学, 大学院・理学研究科, 准教授 (60291085)
• Project Period (FY): 2009 – 2011
• Keywords: 有機金属錯体 / 高周期元素 / ケイ素化学 / 反応化学 / 遷移金属 / シリレン錯体 / ゲルミレン錯体

Research Abstract

Several new silylene complexes having metal-silicon double bonds have been synthesized. Reactivity of these complexes toward various organic substates has been investigated and some new reactions have been found. Reactivity of a hydrido(hydrogermylene)complex has been also studied. Especially, a novel transformation from the germylene complex into a germylyne complex having a W-Ge multiple bond with releasing a hydrogenation product of isocyanate was found.

Research Products

• [Journal Article] Hydrido(hydrosilylene)tungsten Complexes : Dynamic Behavior and Reactivity Toward Acetone (2012)
  • Author(s): Takahito Watanabe, Hisako Hashimoto, Hiromi Tobita
  • Journal Title: Chem. Asian. J. Volume: (印刷中)
  • Peer Reviewed
• [Journal Article] Angew. Formation of a Germylyne Complex : Dehydrogenation of a Hydrido(hydrogermylene)tungsten Complex with Mesityl Isocyanate (2012)
  • Author(s): Hisako Hashimoto, Tetsuya Fukuda, Hiromi Tobita, Mausumi Ray, Shigeyoshi Sakaki
  • Journal Title: Chem. Int. Ed. Volume: 51巻 Pages: 2930-2933
  • Peer Reviewed
• [Journal Article] Reactions of a Neutral Silylene Ruthenium Complex with Heterocumulenes : C=O Hydrosilylation of Isocyanates vs C=S Bond Cleavage of Isothiocyanate (2012)
  • Author(s): Mitsuyoshi. Ochiai, Hisako Hashimoto, Hiromi Tobita
  • Journal Title: Organometallics Volume: 31巻 Pages: 527-530
  • Peer Reviewed
• [Journal Article] Heavier Analogs of Carbene Complexes : Syntheses of a New Type of Silylene and Germylene Complexes and Their Reactions with Unsaturated Organic Compounds (2012)
  • Author(s): 橋本久子, 飛田博実
  • Journal Title: 有機合成化学協会誌 Volume: 70巻 Pages: 131-141
  • Peer Reviewed
• [Journal Article] Experimental and Theoretical Study of a Tungsten Dihydride Silyl Complex : New Insight into Its Bonding Nature and Fluxional Behavior (2010)
  • Author(s): Mausumi. Ray, Yoshihide Nakao, Hirofumi Sato, Shigeyoshi. Sakaki, Takahito Watanabe, Hisako Hashimoto, Hiromi. Tobita
  • Journal Title: Organometallics Volume: 29巻 Pages: 6267-6281
  • Peer Reviewed
• [Journal Article] Synthesis of η2-Cyclooctene Iridium and Rhodium Complexes Supported by a Novel P, N-Chelate Ligand and Their Reactivity toward Hydrosilanes : Facile Cl Migration from Metal to Silicon via Silylene Complex Intermediates and Formation of a Base-Stabilised Silylene (2010)
  • Author(s): Hisako Hashimoto, Toshinori Suzuki, Hiromi Tobita
  • Journal Title: ComplexDalton Trans Volume: 39巻 Pages: 9386-9400
  • Peer Reviewed
• [Journal Article] Reactions of a Hydrido(hydrogermylene)tungsten Complex with Some Heterocumulenes : Hydrogermylation and Thermal Rearrangement (2010)
  • Author(s): Hisako Hashimoto, Tetsuya Fukuda, Hiromi Tobita
  • Journal Title: New J. Chem Volume: 34巻 Pages: 1723-1730
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of a Hydrido(hydrogermylene)tungsten Complex and Its Reactions with Nitriles and Ketones (2009)
  • Author(s): Hisako Hashimoto, Takeshi Tsubota, Tetsuya Fukuda, Hiromi Tobita
  • Journal Title: Chem. Lett Pages: 1196-1197
  • Peer Reviewed
• [Journal Article] Synthesis and Properties of a Silyl(silylene)ruthenium Complex : Activation Barrier of the Ru=Si Bond Rotation and Facile Replacement of the Methyl Groups with Alkoxy Groups of a Silyl Ligand (2009)
  • Author(s): Hisako Hashimoto, Jun Sato, Hiromi Tobita
  • Journal Title: Organometallics Volume: 28巻 Pages: 3963-3965
  • Peer Reviewed
• [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
• [Presentation] (2012)
  • Author(s): 福田哲也, 橋本久子, 飛田博実
  • Organizer: 日本化学会第92春季年会2F7-29
  • Place of Presentation: 日吉
  • Year and Date: 2012-03-26
• [Presentation] 新学術領域研究「分子活性化」 (2012)
  • Author(s): 橋本久子
  • Organizer: 第2回公開シンポジウム
  • Place of Presentation: 日吉
  • Year and Date: 2012-01-19
• [Presentation] (2011)
  • Author(s): 橋本久子, 渡邉孝仁, 飛田博実
  • Organizer: The International Symposium on Organometallic Chemistry 2011 (ISOMC2011)
  • Place of Presentation: 大阪
  • Year and Date: 2011-11-12
• [Presentation] (2011)
  • Author(s): 高木望・小田桐悠斗・橋本久子・飛田博実・榊茂好
  • Organizer: 第61回錯体化学討論会, 2Bb-08
  • Place of Presentation: 岡山
  • Year and Date: 2011-09-18
• [Presentation] (2011)
  • Author(s): 橋本久子, 藤井俊輔, 飛田博実
  • Organizer: 第61回錯体化学討論会, 2Db-20
  • Place of Presentation: 岡山
  • Year and Date: 2011-09-18
• [Presentation] (2011)
  • Author(s): 福田哲也, 橋本久子, 飛田博実
  • Organizer: 第58回有機金属化学討論会, P2C-03
  • Place of Presentation: 名古屋
  • Year and Date: 2011-09-16
• [Presentation] (2011)
  • Author(s): 橋本久子, 小田桐悠斗, 飛田博実, 高木望, 榊茂好
  • Organizer: 第58回有機金属化学討論会, P2C-02
  • Place of Presentation: 名古屋
  • Year and Date: 2011-09-16
• [Presentation] (2011)
  • Author(s): 福田哲也, 橋本久子, 飛田博実
  • Organizer: グローバルCOEサマースクールシンポジウム, P-57
  • Place of Presentation: 仙台
  • Year and Date: 2011-08-18
• [Presentation] (2011)
  • Author(s): 飛田博実, 橋本久子
  • Organizer: The 16th International Symposium on Silicon Chemistry, 274
  • Place of Presentation: Hamilton, Canada
  • Year and Date: 2011-08-15
• [Presentation] 新しいヒドリド(シリレン)タングステン錯体の合成および不飽和化合物との反応 (2011)
  • Author(s): 藤井俊輔, 橋本久子, 飛田博実
  • Organizer: 第91春季年会
  • Place of Presentation: 神奈川
  • Year and Date: 2011-03-26
• [Presentation] (2010)
  • Author(s): 鈴木敏典, 橋本久子, 飛田博実
  • Organizer: 第90春季年会, 2B2-45
  • Place of Presentation: 大阪
  • Year and Date: 20103027
• [Presentation] 大学院GP主催 (2010)
  • Author(s): 鈴木敏典, 橋本久子, 飛田博実
  • Organizer: 第3回東北大学大学院理学研究科6専攻合同シンポジウム
  • Year and Date: 20100200
• [Presentation] The 2010 International Chemical Congress of Pacific Basin Societies (2010)
  • Author(s): 古屋智佳子、橋本久子、飛田博実
  • Organizer: 2010環太平洋国際化学会議
  • Place of Presentation: 米国ハワイ州, ホノルル市
  • Year and Date: 2010-12-16
• [Presentation] (2010)
  • Author(s): 橋本久子、福田哲也、飛田博実、Mausumi Ray、榊茂好
  • Organizer: ケイ素化学協会シンポジウム、P18
  • Place of Presentation: 静岡県湯河原
  • Year and Date: 2010-11-19
• [Presentation] (2010)
  • Author(s): 磯崎政秀, 橋本久子, 飛田博実
  • Organizer: 第60回錯体化学討論会
  • Place of Presentation: 大阪
  • Year and Date: 2010-09-28
• [Presentation] (2010)
  • Author(s): 橋本久子、福田哲也、飛田博実、Mausumi Ray, 榊茂好
  • Organizer: 第57回有機金属化学討論会、P1B-30
  • Place of Presentation: 東京
  • Year and Date: 2010-09-16
• [Presentation] (2010)
  • Author(s): 福田哲也, 橋本久子, 飛田博実
  • Organizer: 第57回有機金属化学討論会, P1B-29
  • Place of Presentation: 東京
  • Year and Date: 2010-09-16
• [Presentation] (2010)
  • Author(s): 福田哲也, 橋本久子, 飛田博実
  • Organizer: Tohoku University Global COE Summer School 2010, P-39
  • Place of Presentation: 仙台
  • Year and Date: 2010-08-19
• [Presentation] (2010)
  • Author(s): 橋本久子, 小田桐悠斗, 松尾里美, 山田康浩, 飛田博実
  • Organizer: 24th International Conference on Organometallic Chemistry (24th ICOMC), PA-075
  • Place of Presentation: 台湾
  • Year and Date: 2010-07-22
• [Presentation] (2010)
  • Author(s): 飛田博実, 橋本久子
  • Organizer: 24th ICOMC Pre-symposia on Organometallic Chemistry
  • Place of Presentation: 台湾
  • Year and Date: 2010-07-19
• [Presentation] (2010)
  • Author(s): 松尾里美, 橋本久子, 飛田博実
  • Organizer: 第90春季年会
  • Place of Presentation: 大阪
  • Year and Date: 2010-03-27
• [Presentation] (2010)
  • Author(s): 福田哲也, 橋本久子, 飛田博実
  • Organizer: 第90春季年会, 2B2-31
  • Place of Presentation: 大阪
  • Year and Date: 2010-03-27
• [Presentation] 特定領域研究 (2010)
  • Author(s): 橋本久子
  • Organizer: 「元素相乗系化合物の化学・第5回公開シンポジウム」
  • Place of Presentation: 京都
  • Year and Date: 2010-03-09
• [Presentation] Molecular Theory for Real Systems (2010)
  • Author(s): 橋本久子, 坪田毅, 福田哲也, 古屋智佳子, 飛田博実
  • Organizer: International Sympojium on
  • Place of Presentation: 京都
  • Year and Date: 2010-01-08
• [Presentation] G-COE Dalian University of Technology (2009)
  • Author(s): 橋本久子
  • Organizer: Tohoku University Joint Symposium
  • Place of Presentation: 仙台
  • Year and Date: 2009-12-09
• [Presentation] (2009)
  • Author(s): 福田哲也, 橋本久子, 飛田博実
  • Organizer: 第59回錯体化学討論会, 2Aa-03
  • Place of Presentation: 長崎
  • Year and Date: 2009-09-26
• [Presentation] (2009)
  • Author(s): 古屋智佳子, 橋本久子, 飛田博実
  • Organizer: 第56回有機金属化学討論会, P3B-09
  • Place of Presentation: 京都
  • Year and Date: 2009-09-11
• [Presentation] (2009)
  • Author(s): 鈴木敏典, 橋本久子, 飛田博実
  • Organizer: 第56回有機金属化学討論会, P3B-32
  • Place of Presentation: 京都
  • Year and Date: 2009-09-11
• [Presentation] (2009)
  • Author(s): 橋本久子, 松山哲也, 飛田博実
  • Organizer: 特定領域研究「実在系の分子理論」第1回公開シンポジウム、P20
  • Place of Presentation: 東京
  • Year and Date: 2009-05-30
• [Remarks]
  • URL: http://inorg.chem.tohoku.ac.jp/