Precise synthesis of cyclic polysilanes and the relative productsvia nickel and palladium key intermediates

• Project/Area Number: 23750059
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Multi-year Fund
• Research Field: Inorganic chemistry
• Research Institution: Tokyo Institute of Technology
• Principal Investigator: TANABE Makoto 東京工業大学, 資源化学研究所, 助教 (80376962)
• Project Period (FY): 2011 – 2012
• Project Status: Completed (Fiscal Year 2012)
• Budget Amount: ¥4,680,000 (Direct Cost: ¥3,600,000、Indirect Cost: ¥1,080,000); Fiscal Year 2012: ¥1,430,000 (Direct Cost: ¥1,100,000、Indirect Cost: ¥330,000); Fiscal Year 2011: ¥3,250,000 (Direct Cost: ¥2,500,000、Indirect Cost: ¥750,000)
• Keywords: 有機金属化学 / 高分子合成 / ポリシラン / 触媒 / 水素 / 合成化学 / 共役分子 / 環状分子 / 電子・電気材料 / ニッケル / π共役 / メタラサイクル / 脱水素カップリング重合 / 固体発光

Research Abstract

This research covers selective preparation between linear and cyclic polysilanes catalyzed by nickel-phosphine catalysts and suggests their reaction mechanism on the basis of chemical properties for the cyclic palladium intermediates. Formation of the cyclic polysilanes and the cyclic intermediates is attributed to be higher thermally stable than the linear one. A new concept of polysilanes involving π-stacking interaction at the side substituents exhibits the unique optical properties.

Research Products

• [Journal Article] Nickel-Catalyzed Cyclopolymerization of Hexyl- and Phenylsilanes (2013)
  • Author(s): 田邊真, 高橋淳, 福田智子, 小坂田耕太郎
  • Journal Title: Organometallics Volume: 32 Issue: 4 Pages: 1037-1043
  • DOI: 10.1021/om301052f
  • Peer Reviewed
• [Journal Article] Dipalladium Complexes with Bridging Monoalkyl or Monophenyl Silyl Ligands in the Solid State and in Solutions (2013)
  • Author(s): 田邊真, 高橋淳, 山田哲行, 小坂田耕太郎
  • Journal Title: Organometallics Volume: 32 Issue: 6 Pages: 1815-1820
  • DOI: 10.1021/om3012486
  • Peer Reviewed
• [Journal Article] Preparation and Properties of Perarylated 3,4-Disila-1,5-hexadienes. A Fluorescent Disilane Accommodated in the Crystal Lattice (2012)
  • Author(s): Makoto Tanabe, Ryouhei Yumoto, Kohtaro Osakada, Takanobu Sanji, Masato Tanaka
  • Journal Title: Organometallics Volume: 31(19) Issue: 19 Pages: 6787-6795
  • DOI: 10.1021/om300551t
  • Peer Reviewed
• [Journal Article] Ring-opening Reaction of a Pergermylated Platinacyclopentane Forming 1,4-Bis(arenethiolato)tetragermanes (2012)
  • Author(s): Makoto Tanabe, Takashi Deguchi, Kohtaro Osakada
  • Journal Title: Organometallics Volume: 31(21) Issue: 21 Pages: 7386-7393
  • DOI: 10.1021/om300655m
  • Peer Reviewed
• [Journal Article] Recent Researches on Activation and Dehydrocoupling of Amine-Boranes at Transition-Metal Centers (2012)
  • Author(s): 田邊真
  • Journal Title: Bull. Jpn. Soc. Coord. Chem. Volume: 60 Pages: 34-47
  • NAID: 130003372876
  • URL: http://dx.doi.org/10.4019/bjscc.60.34
  • Peer Reviewed
• [Journal Article] Reaction of alkyne with dinickel-diphenylsilyl complexes. An emissive disilane formed via the consecutive Si-C and Si-Si bond-making processes (2012)
  • Author(s): 田邊真, 湯本遼平, 小坂田耕太郎
  • Journal Title: Chem. Commun Volume: 48 Issue: 15 Pages: 2125-2127
  • DOI: 10.1039/c2cc16063c
  • Peer Reviewed
• [Journal Article] Recent Researches on Activation and Dehydrocoupling of Amine-Boranes at Transition-Metal Centers (2012)
  • Author(s): Makoto Tanabe
  • Journal Title: Bulletin of Japan Society of Coordination Chemistry Volume: 60 Issue: 0 Pages: 34-37
  • DOI: 10.4019/bjscc.60.34
  • NAID: 130003372876
  • ISSN: 1882-6954, 1883-1737
  • Peer Reviewed
• [Journal Article] Tetrapalladium Complex with Bridging Germylene Ligands [Pd{Pd(dmpe)}_3(μ_3-GePh_2)_3]. Structural Change of the Planar Pd_4Ge_3 Core (2011)
  • Author(s): Makoto Tanabe, Naoko Ishikawa, Mai Chiba, Tomohito Ide, Kohtaro Osakada, Tomoaki Tanase
  • Journal Title: Journal of American Chemical Society Volume: 133 Issue: 46 Pages: 18598-18601
  • DOI: 10.1021/ja208565q
  • Peer Reviewed
• [Journal Article] Dinuclear Palladium and Platinum Complexes with Bridging Silylene Ligands. Preparation using (Aminosilyl)boronic Ester as the Ligand Precursor and Their Reactions with Alkynes (2011)
  • Author(s): 田邊真, Jian Jiang, 山澤英人, 小坂田耕太郎, 大村智通, 杉野目道紀
  • Journal Title: Organometallics Volume: 30 Issue: 15 Pages: 3981-3991
  • DOI: 10.1021/om200156g
  • Peer Reviewed
• [Journal Article] Chemical Properties of Tetragermaplatina- cyclopentane. Insertion of an Alkyne into a Pt-Ge Bond and Silylation Caused by H2 SiPh 2 (2011)
  • Author(s): 田邊真, 出口尚史, 小坂田耕太郎
  • Journal Title: Organometallics Volume: 30 Issue: 12 Pages: 3386-3391
  • DOI: 10.1021/om200275w
  • Peer Reviewed
• [Journal Article] Cd(II) and Pb(II) Complexes of the Polyether IonophorusAntibiotic Salinomycin (2011)
  • Author(s): Juliana Ivanova, Ivayla N. Pantcheva, Mariana Mitewa, Svetlana Simova, 田邊真, 小坂田耕太郎
  • Journal Title: Chem. Cent. J. Volume: 5 Issue: 1 Pages: 52-52
  • DOI: 10.1186/1752-153x-5-52
  • Peer Reviewed
• [Journal Article] IR and DFT studies of phenylplatinum complexes with O-monodentate coordinated silsesquioxanate and auxiliary phosphine ligands (2011)
  • Author(s): Neli Mintcheva, Ivelina Georgieva, Tzvetan Mihaylov, Natasha Trendafilova, 田邊真, 小坂田耕太郎, NMR
  • Journal Title: J. Organomet. Chem. Volume: 697 Issue: 1 Pages: 23-32
  • DOI: 10.1016/j.jorganchem.2011.09.023
  • Peer Reviewed
• [Presentation] 環状遷移金属錯体を利用するオリゴゲルマンの末端官能基化 (2013)
  • Author(s): 田邊真,出口尚史,高橋淳,小坂田耕太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学
• [Presentation] 橋架けゲルミレン-パラジウム二核錯体の合成と分子構造評価 (2013)
  • Author(s): 大嶺俊平,田邊真,小坂田耕太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学
• [Presentation] 橋架けシリレン-パラジウム,白金二核錯体の合成と不飽和有機分子との反応 (2013)
  • Author(s): 金子暁,酒井優,田邊真,小坂田耕太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学
• [Presentation] Dehydrocoupling Reactions of Organosilanes and Organogermanes using Late Transition Metal Catalysts (2013)
  • Author(s): Makoto Tanabe，Kohtaro Osakada
  • Organizer: 5th Gratama workshop
  • Place of Presentation: 東京工業大学 大岡山キャンパス
• [Presentation] 後周期遷移金属錯体による有機ケイ素化合物の環化重合 (2013)
  • Author(s): 田邊 真，高橋 淳，小坂田 耕太郎
  • Organizer: 第62回高分子学会年次大会
  • Place of Presentation: 京都国際会館
• [Presentation] 環状遷移金属錯体を利用するオリゴゲルマンの末端官能基化 (2013)
  • Author(s): 田邊 真，出口 尚史，高橋 淳，小坂田 耕太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス
• [Presentation] 橋架けゲルミレン-パラジウム二核錯体の合成と分子構造評価 (2013)
  • Author(s): 大嶺 俊平，田邊 真，小坂田 耕太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス
• [Presentation] 橋架けシリレン-パラジウム、白金二核錯体の合成と不飽和有機分子との反応 (2013)
  • Author(s): 金子 暁，酒井 優，田邊 真，小坂田 耕太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス
• [Presentation] 10族遷移金属錯体を中間体とする鎖及び環状有機ケイ素高分子の選択的合成 (2013)
  • Author(s): 高橋 淳，田邊 真，小坂田 耕太郎
  • Organizer: 日本化学会第93春季年会
  • Place of Presentation: 立命館大学びわこ・くさつキャンパス
• [Presentation] Group10 Transition Metal Complexes with Bridging Si Ligands: Their Unique Structures and Chemical Properties (2012)
  • Author(s): 田邊真,湯本遼平,小坂田耕太郎
  • Organizer: 4th Asian Silicon Symposium (ASIS-4)
  • Place of Presentation: つくば国際会議場
• [Presentation] Di- or Trinuclear Transition Metal Complexes with Germylene Ligands Leading to the Ge-Ge Bond Formations (2012)
  • Author(s): 大嶺俊平,田邊真,小坂田耕太郎
  • Organizer: 4th Asian Silicon Symposium (ASIS-4)
  • Place of Presentation: つくば国際会議場.
• [Presentation] Nickel-Catalyzed Dehydrocoupling of Primary and Secondary Silanes: Selective Formation of Linear and Cyclic Polysilanes (2012)
  • Author(s): 高橋淳,田邊真,小坂田耕太郎
  • Organizer: 4th Asian Silicon Symposium (ASIS-4)
  • Place of Presentation: つくば国際会議場
• [Presentation] Ni,Pd錯体触媒によるケイ素高分子の鎖と環の構造規制:σ-π共役型ポリシランへの展開 (2012)
  • Author(s): 高橋淳,田邊真,小坂田耕太郎
  • Organizer: 第62回錯体化学会討論会
  • Place of Presentation: 富山大学
• [Presentation] Dinuclear Complexes with Bridging Silylene or Silyl Ligands. Their Unique Structures and Reactivity Toward Alkynes (2012)
  • Author(s): 田邊真 ,小坂田耕太郎
  • Organizer: 44th Silicon Symposium
  • Place of Presentation: Brock University,Ontario,Canada.
• [Presentation] 環状遷移金属錯体を鍵中間体とするオリゴゲルマンの効率的合成とその性質 (2012)
  • Author(s): 田邊真,出口尚史,小坂田耕太郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学
• [Presentation] 新規ケイ素架橋ニッケル二核錯体と分子内Si-Si結合形成を経由する発光性ジシランの合成 (2012)
  • Author(s): 湯本遼平,田邊真,小坂田耕太郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学
• [Presentation] ヒドロシランの触媒的環化カップリ ング重合とその反応機構 (2012)
  • Author(s): 高橋淳,福田智子,田邊真,小坂田耕太郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学
• [Presentation] 高周期14族元素が橋架けする多 核遷移金属錯体の合成と変換反応 (2012)
  • Author(s): 田邊真
  • Organizer: 第八回有機元素化学セミナー
  • Place of Presentation: 京都大学
• [Presentation] ケイ素化合物を配位子,単量体とする新しい遷移金属錯体,高分子の合成 (2012)
  • Author(s): 田邊真
  • Organizer: 第15回ケイ素化学協会シンポジウム
  • Place of Presentation: 兵庫
• [Presentation] ケイ素-ニッケルニ核錯体とアルキンとの反応によるσ-π共役分子の合成と発光挙動 (2012)
  • Author(s): 湯本遼平,田邊真,小坂田耕太郎
  • Organizer: 第15回ケイ素化学協会シンポジウム
  • Place of Presentation: 兵庫
• [Presentation] 環状白金錯体による有機ゲルマニウムオリゴマーの効率的合成と発光挙動 (2012)
  • Author(s): 出口尚史,土戸良高,須崎裕司,田邊真,小坂田耕太郎
  • Organizer: 第61回錯体化学会討論会
  • Place of Presentation: 岡山理科大学
• [Presentation] Preparation and Properties of the Metallacycloalkanes Composed of Heavier Group 14 Elements (2012)
  • Author(s): 田邊真,小坂田耕太郎
  • Organizer: 94th Canadian Chemistry Conference and Exhibition
  • Place of Presentation: Montreal, Canada.
• [Presentation] Group 10 Transition Metal Complexes with Bridging Si Ligands: Their Unique Structures and Chemical Properties (2012)
  • Author(s): Makoto Tanabe，Ryouhei Yumoto，Kohtaro Osakada
  • Organizer: 4th Asian Silicon Symposium (ASIS-4)
  • Place of Presentation: つくば国際会議場
• [Presentation] Di- or Trinuclear Transition Metal Complexes with Germylene Ligands Leading to the Ge－Ge Bond Formations (2012)
  • Author(s): Shumpei Omine，Makoto Tanabe，Kohtaro Osakada
  • Organizer: 4th Asian Silicon Symposium (ASIS-4)
  • Place of Presentation: つくば国際会議場
• [Presentation] Preparation of Unsaturated Dinuclear Pd and Pt Complexes with Bridging Silylene Ligands Using (Aminosilyl)boronic Ester (2012)
  • Author(s): Akira Kaneko，Masaru Sakai，Makoto Tanabe，Kohtaro Osakada
  • Organizer: 4th Asian Silicon Symposium (ASIS-4)
  • Place of Presentation: つくば国際会議場
• [Presentation] ゲルミレン-遷移金属多核錯体の合成とGe－Ge間結合形成の考察 (2012)
  • Author(s): 大嶺 俊平，田邊 真，小坂田 耕太郎
  • Organizer: 第62回錯体化学会討論会
  • Place of Presentation: 富山大学 五福キャンパス
• [Presentation] Ni, Pd錯体触媒によるケイ素高分子の鎖と環の構造規制：σ－π共役型ポリシランへの展開 (2012)
  • Author(s): 高橋 淳，田邊 真，小坂田 耕太郎
  • Organizer: 第62回錯体化学会討論会
  • Place of Presentation: 富山大学 五福キャンパス
• [Presentation] Dinuclear Complexes with Bridging Silylene or Silyl Ligands. Their Unique Structures and Reactivity Toward Alkynes (2012)
  • Author(s): Makoto Tanabe，Kohtaro Osakada
  • Organizer: 44th Silicon Symposium
  • Place of Presentation: Brock University, Ontario, Canada
• [Presentation] Heterometallic Tetranuclear Complexes with Bridging Silylene Ligands. Self-Assembled Formation of the PtPd3Si3 Core (2012)
  • Author(s): Makoto Tanabe，Kohtaro Osakada
  • Organizer: 44th Silicon Symposium
  • Place of Presentation: Brock University, Ontario, Canada
• [Presentation] 環状遷移金属錯体を鍵中間体とするオリゴゲルマンの効率的合成とその性質 (2012)
  • Author(s): 田邊 真, 出口 尚史, 小坂田 耕太郎
  • Organizer: 日本化学会第92春季年会
  • Place of Presentation: 慶応大学、横浜
• [Presentation] 高周期14族元素が橋架けする多核遷移金属錯体の合成と変換反応 (2011)
  • Author(s): 田邊 真
  • Organizer: 第八回有機元素化学セミナー(招待講演)
  • Place of Presentation: 京都大学、宇治
• [Presentation] ケイ素化合物を配位子、単量体とする新しい遷移金属錯体、高分子の合成 (2011)
  • Author(s): 田邊 真
  • Organizer: 第15回ケイ素化学協会シンポジウム(招待講演)
  • Place of Presentation: シーパル須磨、兵庫
• [Presentation] Preparation and Properties of the Metallacycloalkanes Composed of Heavier Group 14 Elements (2011)
  • Author(s): Makoto Tanabe, Kohtaro Osakada
  • Organizer: 94th Canadian Chemistry Conference and Exhibition(招待講演)
  • Place of Presentation: Montreal, Canada