Synthesis of low-valent silicon compounds by the facile preparation of bulky alkyl groups

• Project/Area Number: 25620020
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Tohoku University
• Principal Investigator: ISHIDA Shintaro 東北大学, 理学(系)研究科(研究院), 講師 (90436080)
• Project Period (FY): 2013-04-01 – 2015-03-31
• Project Status: Completed (Fiscal Year 2014)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2014: ¥1,820,000 (Direct Cost: ¥1,400,000、Indirect Cost: ¥420,000); Fiscal Year 2013: ¥2,210,000 (Direct Cost: ¥1,700,000、Indirect Cost: ¥510,000)
• Keywords: ケイ素 / 低配位化合物 / アルキル基 / ジシリン / 遷移金属錯体 / 速度論的安定化 / 低配位ケイ素化合物 / シリリン / ジシラビニリデン / ジシラシクロブタジエン

Outline of Final Research Achievements

(1) A new isolable dialkyldisilyne was fully characterized. Thermolysis of the dialkyldisilyne gave not the corresponding silylyne but bi(silacyclopropane)s. Disilyne- palladium and platinum complexes are successfully obtained by the ligand exchange reactions. The isolable disilyne coordinates to the transition metals in a side-on fashion and these complexes has trans-bent geometry in contrast to the corresponding alkyne complexes. These complexes showed significant metallacycle character.
(2) A tetraalkyl-substituted spiropentasiladiene was newly synthesized and characterized. The tetraalkylspiropentasiladiene show several absorption bands around 320-450 nm in solution due to non-degenerated HOMO/HOMO-1 and LUMO/LUMO+1. Chlorination and ring expansion reaction of spiropentasiladiene were conducted.

Research Products

• [Journal Article] Unexpected Formation of Highly Strained 2,5-Dioxa-Silabicyclo[2.1.0]Pentane by the Reaction of Isolable Dialkylsilylene with Benzil (2014)
  • Author(s): Shintaro Ishida, Kenya Uchida, Takeaki Iwamoto
  • Journal Title: Heteroatom Chemistry Volume: 25 Issue: 5 Pages: 348-353
  • DOI: 10.1002/hc.21162
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Isolable 2,3-Disila-1,3-butadiene via Double Sila-Peterson Reaction (2014)
  • Author(s): Daiki Motomatsu, Shintaro Ishida, Koichi Ohno, Takeaki Iwamoto
  • Journal Title: Chem. Eur. J. Volume: 20 Issue: 30 Pages: 9424-9430
  • DOI: 10.1002/chem.201402868
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Persistent Antimony- and Bismuth-Centered Radicals in Solution (2014)
  • Author(s): 石田真太郎、平川文弥、古川 貢、与座健治、岩本武明
  • Journal Title: Angewandte Chemie International Edition Volume: 53 Issue: 42 Pages: 11172-11176
  • DOI: 10.1002/anie.201405509
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A heavy analogue of the smallest bridgehead alkene stabilized by a base (2014)
  • Author(s): Takeaki Iwamoto, Naohiko Akasaka, Shintaro Ishida
  • Journal Title: Nat. Commun. Volume: 5 Issue: 1 Pages: 5353-5353
  • DOI: 10.1038/ncomms6353
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Near-IR Absorbing Nickel(II) Porphyrinoids Prepared by Regioselective Insertion of Silylenes into Antiaromatic Nickel(II) Norcorrole (2014)
  • Author(s): Takaki Fukuoka, Kenya Uchida, Young Mo Sung, Ji-Young Shin, Shintaro Ishida, Dr. Jong Min Lim, Satoru Hiroto, Ko Furukawa, Dongho Kim, Takeaki Iwamoto, Hiroshi Shinokubo
  • Journal Title: Angewandte Chemie, International Edition Volume: 53 Issue: 6 Pages: 1506-1509
  • DOI: 10.1002/anie.201309921
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Silicon Compounds with Inverted Geometry around Silicon Atoms (2014)
  • Author(s): Takeaki Iwamoto, Shintaro Ishida
  • Journal Title: Chemistry Letters Volume: 43 Issue: 2 Pages: 164-170
  • DOI: 10.1246/cl.130856
  • NAID: 130004867960
  • Peer Reviewed
• [Journal Article] Palladium and Platinum η2-Disilyne Complexes Bearing an Isolable Dialkyldisilyne as a Ligand (2013)
  • Author(s): Shintaro Ishida, Ryutaro Sugawara, Yoshifumi Misawa and Takeaki Iwamoto
  • Journal Title: Angew. Chem. Int. Ed. (Selected as a Very Important Paper) Volume: 52 Issue: 49 Pages: 12869-12873
  • DOI: 10.1002/anie.201308517
  • Peer Reviewed
• [Journal Article] Anthryl-substituted 3-Silylene-2-silaaziridine Obtained by Isomerization of Disilacyclopropanimine: An Exocyclic Silene Showing Distinct Intramolecular Charge Transfer Transition (2013)
  • Author(s): Takeaki Iwamoto, Nobuyoshi Ohnishi, Naohiko Akasaka, Koichi Ohno, Shintaro Ishida
  • Journal Title: Journal of the American Chemical Society Volume: 135 Issue: 29 Pages: 10606-10609
  • DOI: 10.1021/ja404045f
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] ベンゾジシラシクロブタジエンの合成と性質 (2014)
  • Author(s): 石田真太郎、三澤祥文、岩本武明
  • Organizer: 第41回有機典型元素化学討論会
  • Place of Presentation: 宇部市文化会館、宇部
  • Year and Date: 2014-11-27 – 2014-11-29
• [Presentation] Palladium and Platinum Complexes of an Isolable Dialkyldisilyne (2014)
  • Author(s): Shintaro Ishida
  • Organizer: The 16th Japan-Korea Joint Symposium on Organometallic and Coordination Chemistry
  • Place of Presentation: Katahira Sakura Hall, Tohoku University, Sendai
  • Year and Date: 2014-10-23 – 2014-10-25
  • Invited
• [Presentation] Palladium and Platinum Complexes of an Isolable Silicon-Silicon Triply Bonded Compound (2014)
  • Author(s): Shintaro Ishida, Ryutaro Sugawara, Yoshifumi Misawa, and Takeaki Iwamoto
  • Organizer: The 17th International Symposium on Silicon Chemistry 2014 Berlin & the 7th European Silicon Days
  • Place of Presentation: Technische Universitat Berlin, Berlin, Germany
  • Year and Date: 2014-08-03 – 2014-08-08
• [Presentation] Palladium and Platinum Complexes of an Isolable Silicon-Silicon Triply Bonded Compound (2014)
  • Author(s): Shintaro Ishida, Ryutaro Sugawara, Yoshifumi Misawa, and Takeaki Iwamoto
  • Organizer: International Conference on Organometallic Chemistry (ICOMC) 2014 Pre-Symposium in Sendai
  • Place of Presentation: Center Hall, School of Engineering, Tohoku University, Sendai
  • Year and Date: 2014-07-11
  • Invited
• [Presentation] Reactions of an Isolable Dialkylsilylene with Substituted Benzophenones (2014)
  • Author(s): Shintaro Ishida, Kenya Uchida, Takeaki Iwamoto
  • Organizer: The International Symposium on Reactive Intermediates and Unusual Molecules (ISRIUM) 2014
  • Place of Presentation: The Aster Plaza, Hiroshima
  • Year and Date: 2014-04-01 – 2014-04-06
• [Presentation] 安定シリレンの特徴的な反応を利用した新規含ケイ素π電子系の創製
  • Author(s): 石田真太郎
  • Organizer: 第17回ケイ素化学協会シンポジウム
  • Place of Presentation: 箱根湯本温泉ホテルおかだ,神奈川
  • Invited
• [Presentation] Synthesis, Structures, and Properties of η2-Disilyne Palladium and Platinum Complexes
  • Author(s): Yoshifumi Misawa, Ryutaro Sugawara, Shintaro Ishida, Takeaki Iwamoto
  • Organizer: International Symposium for the 70th Anniversary of the Tohoku Branch of the Chemical Society of Japan
  • Place of Presentation: Tohoku University, Sendai
• [Presentation] Isolable Dialkylsilylene That Equilibrates with Its Isolable Dimer in Solution
  • Author(s): Shintaro Ishida, Takashi Abe, Ryoji Tanaka, Mitsuo Kira, Takeaki Iwamoto
  • Organizer: 4th UK/Japan Conference in Catalytic Asymmetric Synthesis
  • Place of Presentation: Sendai International Centre, Sendai
• [Presentation] η 2 -ジシリン 10 族遷移金属錯体の構造と性質
  • Author(s): 三澤祥文、菅原隆太郎、石田真太郎、岩本武明
  • Organizer: 第17回ケイ素化学協会シンポジウム
  • Place of Presentation: 箱根湯本温泉ホテルおかだ,神奈川
• [Book] 現代ケイ素化学（吉良満夫・玉尾皓平 編） 第５章・シリレン (2013)
  • Author(s): 石田真太郎・岩本武明
  • Total Pages: 472
  • Publisher: 化学同人
• [Book] 現代ケイ素化学（吉良満夫・玉尾皓平 編） 第18章・シリル転位反応 (2013)
  • Author(s): 岩本武明・石田真太郎
  • Total Pages: 472
  • Publisher: 化学同人
• [Book] Functional Molecular Silicon Compounds II (D. Scheschkewitz Ed.): Multiple Bonds with Silicon: Recent Advances in Synthesis, Structure, and Functions of Stable Disilenes (2013)
  • Author(s): Takeaki Iwamoto, Shintaro Ishida
  • Total Pages: 232
  • Publisher: Springer