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

• 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
• Project Status: Completed (Fiscal Year 2011)
• Budget Amount: ¥4,810,000 (Direct Cost: ¥3,700,000、Indirect Cost: ¥1,110,000); Fiscal Year 2011: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2010: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2009: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000)
• 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
  • NAID: 10030481285
  • Peer Reviewed
• [Journal Article] Hydrido(hydrosilylene)tungsten Complexes : Dynamic Behavior and Reactivity Toward Acetone (2012)
  • Author(s): Takahito Watanabe, Hisako Hashimoto, Hiromi Tobita
  • Journal Title: Chemistry-An Asian Journal Volume: (未定)(印刷中) Issue: 6 Pages: 1408-1416
  • DOI: 10.1002/asia.201101058
  • Peer Reviewed
• [Journal Article] 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, Sakaki Shigeyoshi
  • Journal Title: Angewandte Chemie International Edition Volume: 51 Issue: 12 Pages: 2930-2933
  • DOI: 10.1002/anie.201107501
  • Peer Reviewed
• [Journal Article] カルベン錯体の高周期類縁体:新規シリレンおよびゲルミレン錯体の合成と不飽和有機化合物との反応 (2012)
  • Author(s): 橋本久子, 飛田博実
  • Journal Title: 有機合成化学協会誌 Volume: 70 Pages: 131-141
  • NAID: 10030481285
  • 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] Reactions of a Hydrido (hydrogermylene) tungsten Complex with Some Heterocumulenes : Hydrogermylation and Thermal Rearrangement (2010)
  • Author(s): Hisako Hashimoto, et al
  • Journal Title: New Journal of Chemistry Volume: 34 Pages: 1723-1730
  • Peer Reviewed
• [Journal Article] Synthesis of η^2-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 Complex (2010)
  • Author(s): Hisako Hashimoto, et al
  • Journal Title: Dalton Transactions Volume: 39 Pages: 9386-9400
  • Peer Reviewed
• [Journal Article] Experimental and Theoretical Study of Tungsten Dihydride Silyl Compiex : New Insight into Their Bonding Nature and Fluxional Behavior (2010)
  • Author(s): Mausui Ray, et al
  • Journal Title: Organometallics Volume: 29 Pages: 6267-6281
  • 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
  • NAID: 10027176045
  • 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
• [Journal Article] Reactions of a Hydrido(hydrosilylene)ruthenium Complex with Carbonyl Compounds (2009)
  • Author(s): Mitsuyoshi Ochiai, et al.
  • Journal Title: Dalton Transactions Pages: 1812-1814
  • 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, et al.
  • Journal Title: Organometallics 28 Pages: 3963-3965
  • 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, et al.
  • Journal Title: Chemistry Letters Pages: 1196-1197
  • NAID: 10027176045
  • 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] 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有機化合物との反応 (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
  • Place of Presentation: 岡山
  • Year and Date: 2011-09-18
• [Presentation] 水素架橋したビス(シリレン)タングステン錯体の動的挙動に関する理論的研究 (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
  • 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] Conversion of a W-Ge Double bond into a W-Ge Triple bond : Formation of a Germylyne Complex and Its Reactivity (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
  • Place of Presentation: 名古屋
  • Year and Date: 2011-09-08
• [Presentation] Spectroscopic and Theoretical Studies on the Dynamic Behavior of a Hydrogen-Bridged Bis(silylene)tungsten Complex (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
  • Place of Presentation: 名古屋
  • Year and Date: 2011-09-08
• [Presentation] Spectroscopic and Theoretical Studies on the Dynamic Behavior of a Hydrogen-Bridged Bis (silylene) tungsten Complex (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
  • Place of Presentation: 名古屋
  • Year and Date: 2011-09-08
• [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] 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] Reactions of a hydrido (hydrogermylene) tungsten complex with isothiocyanates and isocyanates (2010)
  • Author(s): 福田哲也、橋本久子、飛田博実
  • Organizer: 2010環太平洋国際化学会議(The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ホノルル、米国
  • Year and Date: 2010-12-16
• [Presentation] Synthesis and Reactions of a hydrido (hydrogermylene) ruthenium complex with several unsaturated compounds (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(The 2010 International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: ホノルル、米国
  • 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] ヒドリド(ヒドロゲルミレン)タングステン錯体とメシチルイソシアナートとの反応:脱水素によるゲルミリン錯体の生成とその反応機構 (2010)
  • Author(s): 橋本久子、福田哲也、飛田博実、Mausunmi Ray、榊茂好
  • Organizer: ケイ素化学協会シンポジウム
  • 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] エチニル基によって架橋されたビス(シリレン)タングステン錯体の構造に関する理論的予測 (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] Dehydrogenation of a Hydrido (hydrogermylene) tungsten Complex with Mesitylisocyanate to Form a Germylyne Complex : NMR and Theoretical Studies on the Reaction Mechanism (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
  • Place of Presentation: 東京
  • Year and Date: 2010-09-16
• [Presentation] Reactions of a Hydrido (hydrogermylene) tungsten Complex with Some Carboxylic Acids (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
  • 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] Synthesis and Peculiar Properties of Hydrogen-Bridged Bis (silylene) tungsten Complexes : A Novel Bonding Mode, Dynamic Behavior, and High Reactivity (2010)
  • Author(s): Hisako Hashimoto, Yuto Odagiri, Satomi Matsuo, Yasuhiro Yamada, Hiromi Tobita
  • Organizer: 24^<th> International Conference on Organometallic Chemistry (24^<th> ICOMC)
  • Place of Presentation: Taipei,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] (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
• [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
• [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] Reactivity of Neutral Silylene and Germylene Transition Metal Complexes Having M-H and E-H(E=Si, Ge)Bonds Toward Unsaturated Organ is Compounds (2009)
  • Author(s): Hisako Hashimoto
  • Organizer: G-COE Dalian University of Technology-Tohoku University
  • Place of Presentation: 川内萩ホール(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/