Iron-catalyzed dehydrogenative coupling of tertiary silanes and the reactivity of intermediates

• Project/Area Number: 20750049
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Inorganic chemistry
• Research Institution: Osaka City University
• Principal Investigator: ITAZAKI Masumi Osaka City University, 大学院・理学研究科, 講師 (60382032)
• Project Period (FY): 2008 – 2009
• Project Status: Completed (Fiscal Year 2009)
• Budget Amount: ¥4,420,000 (Direct Cost: ¥3,400,000、Indirect Cost: ¥1,020,000); Fiscal Year 2009: ¥1,950,000 (Direct Cost: ¥1,500,000、Indirect Cost: ¥450,000); Fiscal Year 2008: ¥2,470,000 (Direct Cost: ¥1,900,000、Indirect Cost: ¥570,000)
• Keywords: 鉄錯体 / ヒドロシラン / 光反応 / カップリング反応 / ジメチルホルムアミド / ガップリング反応 / 置換反応 / 脱水素カップリング / Si-Si結合形成反応

Research Abstract

We found photoreaction of tertiary silanes R3SiH in DMF to produce the corresponding disiloxanes R_3Si-O-SiR_3. The consideration of catalytic reaction pathway revealed a hydridodisilyliron (IV) complex is an intermediate. In addition, unprecedented hydridoiron (IV) complexes with two different Group 14 element ligands Cp(CO)Fe(H)(EEt_3)(E'Et_3)(E, E'=Si, Ge, Sn) were isolated and characterized. The reaction of these complexes with Et_3E''H revealed the tendency of reductive elimination of Et_3EH from the central iron.

Research Products

• [Journal Article] Platinum complexes with diamino-substituted phosphorus ligands: synthesis, characterization, and their reactivity with a Lewis acid (2010)
  • Author(s): Masumi Itazaki, Yuka Shigesato, Hiroshi Nakazawa
  • Journal Title: C.R. Chim. (in press)
  • Peer Reviewed
• [Journal Article] Synthesis, Characterization, and Crystal Structure of Germyl- (phosphine)iron Complexes, Cp(CO)Fe- (PPh3)(GeR3) (R = Et, nBu, Ph), Prepared from Cp(CO)Fe(PPh3)(Me) and HGeR3 (2010)
  • Author(s): Masumi Itazaki, Masahiro Kamitani, Yasuhiro Hashimoto, Hiroshi Nakazawa
  • Journal Title: Phosphorus, Sulfur Silicon Relat. Elem. 185 Pages: 1054-160
  • Peer Reviewed
• [Journal Article] Platinum complexes with diamino-substituted phosphorus ligands : synthesis, characterization, and their reactivity with a Lewis acid (2010)
  • Author(s): Masumi Itazaki, Yuka Shigesato, Hiroshi Nakazawa
  • Journal Title: C.R.Chim. (in press)
  • Peer Reviewed
• [Journal Article] Iron-Catalyzed Dehygro- genative Coupling of Tertiary Silanes (2009)
  • Author(s): Masumi Itazaki, Kensuke Ueda, Hiroshi Nakazawa
  • Journal Title: Angew. Chem., Int. Ed. 48 Pages: 3313-3316
  • Peer Reviewed
• [Journal Article] Syntheses and Ligand Exchange Reaction of Iron(IV) Complexes with Two Different Group 14 Element Ligands, Cp(CO)FeH(EEt3)(E'Et3) (E, E' = Si, Ge, Sn) (2009)
  • Author(s): Masumi Itazaki, Masahiro Kamitani, Kensuke Ueda, Hiroshi Nakazawa
  • Journal Title: Organometallics 28 Pages: 3601-3603
  • Peer Reviewed
• [Journal Article] Iron-Catalyzed Dehygrogenative Coupling of Tertiary Silanes (2009)
  • Author(s): Masumi Itazaki, Kensuke Ueda, Hiroshi Nakazawa
  • Journal Title: Angew.Chem., Int. Ed. 48 Pages: 6938-6938
  • Peer Reviewed
• [Journal Article] Syntheses and Ligand Exchange Reaction of Iron(IV) Complexes with Two Different Group 14 Element Ligands, Cp(CO)FeH(EEt_3)(E'Et_3) (E, E'=Si,Ge,Sn) (2009)
  • Author(s): Masumi Itazaki, Masahiro Kamitani, Kensuke Ueda, Hiroshi Nakazawa
  • Journal Title: Organometallics 28 Pages: 3601-3603
  • Peer Reviewed
• [Journal Article] Synthesis, Characterization, and Crystal Structure of Germyl(phosphine)iron Complexes, Cp(CO)Fe(PPh_3)(GeR_3)(R=Et, ^<n>Bu, Ph), Prepared from Cp(CO)Fe(PPh_3)(Me)and HGeR_3 (2009)
  • Author(s): Masumi Itazaki, Masahirc Kamitani, Yasuhiro Hashimoto, Hiroshi Nakazawa
  • Journal Title: Phosphorus, Sulfur Silicon Relat. Elem 184(in press)
  • Peer Reviewed
• [Journal Article] Iron-Catalyzed Dehydrogenative Coupling of Tertiary Silanes (2009)
  • Author(s): Masumi Itazaki, Kensuke Ueda, Hiroshi Nakazawa
  • Journal Title: Angew. Chem., Int. Ed 48 Pages: 3313-3316
  • Peer Reviewed
• [Journal Article] [(Carbonyl)- (η5-cyclopentadienyl)(triethylstannyl)- (pyridine) iron(II)] (2008)
  • Author(s): Masumi Itazaki, Masahiro Kamitani, Hiroshi Nakazawa
  • Journal Title: Acta Crystallogr. E64
  • Peer Reviewed
• [Journal Article] (Carbonyl)(h^<5-> cyclopentadienyl)(triethylstannyl)(pyridine)iron(II) (2008)
  • Author(s): Masumi Itazaki, Masahiro Kamitani Hiroshi Nakazawa
  • Journal Title: Acta Crystallogr E64
  • Peer Reviewed
• [Presentation] Dehydr ogenative Coupling of Hydrogermane Catalyzed byan Iron Complex (2009)
  • Author(s): 神谷昌宏、板崎真澄、中沢浩
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学今出川キャンパス
• [Presentation] Catalytic Behavior of Cp(CO)2FeMe in Hydrosilylation and Dehydrogenative Silylation of Olefins (2009)
  • Author(s): oman N. Naumov、板崎真澄、中沢浩
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学文教キャンパス
• [Presentation] 鉄4価ビスシリルヒドリド錯体の合成とそれを用いたヒドロシランのポリマー化反応 (2009)
  • Author(s): 橋本康弘、神谷昌宏、板崎真澄、中沢浩
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学文教キャンパス
• [Presentation] 鉄錯体を触媒とするチオールの選択的変換反応 (2009)
  • Author(s): 板崎真澄、中村渉、神谷昌宏、中沢浩
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学文教キャンパス
• [Presentation] 鉄メチル錯体を触媒とする選択的なEO- Ge (E = Si, Ge, Sn)結合生成反応 (2009)
  • Author(s): 神谷昌弘、夛田亮祐、板崎真澄、中沢浩
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパ
• [Presentation] リン配位子を有する鉄メチル錯体の合成とそのヒドロゲルマンに対する反応性 (2009)
  • Author(s): 板崎真澄、橋本康弘、神谷昌弘、中沢浩
  • Organizer: 日本化学会第89春季年会
  • Place of Presentation: 日本大学船橋キャンパス、千葉
• [Presentation] Dehydrogenative Coupling of Hydrogenmane Catalyzed by an Iron Complex (2009)
  • Author(s): 神谷昌宏、板崎真澄、中沢浩
  • Organizer: 第56回有機金属化学討論会
  • Place of Presentation: 同志社大学今出川キャンパス
• [Presentation] Catalytic Behavior of Cp(CO)_2FeMe in Hydrosilylation and Dehydrogenative Silylation of Olefins (2009)
  • Author(s): Roman N.Naumov, 板崎真澄, 中沢浩
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学文教キャンパス
• [Presentation] 鉄メチル錯体を触媒とする選択的なE-O-Ge(E=Si,Ge,Sn)結合生成反応 (2009)
  • Author(s): 神谷昌弘、夛田亮祐、板崎真澄、中沢浩
  • Organizer: 日本化学会第90春季年会
  • Place of Presentation: 近畿大学本部キャンパス
• [Presentation] Dehydrogenative Silyl Coupling Reactions catalyzed by an Iron Complex (2008)
  • Author(s): H. Nakazawa, M. Itazaki, K. Ueda
  • Organizer: The 15th International Symposium on Organosilicon Chemistry
  • Place of Presentation: Jeju, Korea
• [Presentation] Iron Complex Catalyst for Si-Si Bond Formation (2008)
  • Author(s): H. Nakazawa, M. Itazaki, K. Ueda
  • Organizer: 23th International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes, France
• [Presentation] Iron Complex Catalyst for Si- Si Bond Formation (2008)
  • Author(s): H. Nakazawa, M. Itazaki, and K. Ueda
  • Organizer: 23th International Conference on Organometallic Chemistry
  • Place of Presentation: Rennes, France
• [Remarks]
  • URL: http://www.sci.osaka-cu.acjp/chem/cc/index.html