Development of the chemistry of silicon-containing antiaromatic compounds by the versatile synthetic method for benzodisilacyclobutadienes

• Project/Area Number: 15K13635
• Research Category: Grant-in-Aid for Challenging Exploratory Research
• Allocation Type: Multi-year Fund
• Research Field: Organic chemistry
• Research Institution: Tohoku University
• Principal Investigator: Shintaro Ishida 東北大学, 理学研究科, 准教授 (90436080)
• Project Period (FY): 2015-04-01 – 2018-03-31
• Project Status: Completed (Fiscal Year 2017)
• Budget Amount: ¥4,030,000 (Direct Cost: ¥3,100,000、Indirect Cost: ¥930,000); Fiscal Year 2017: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2016: ¥1,170,000 (Direct Cost: ¥900,000、Indirect Cost: ¥270,000); Fiscal Year 2015: ¥1,690,000 (Direct Cost: ¥1,300,000、Indirect Cost: ¥390,000)
• Keywords: 反芳香族 / ケイ素 / リン / 環状π電子系 / ホスファジシリレン / ベンゾジシラシクロブタジエン / 反芳香族性 / π電子系 / ジシレン / ジシラシクロブタジエン / ジシリン / シリン / 速度論的安定化

Outline of Final Research Achievements

Silicon-containing cyclic 4npi-electron systems were constructed and their characteristics were revealed. We successfully synthesized benzodisilacyclobutadienes, which exhibited a significant contribution of a 1,2-disilacyclobutadiene resonance structure. We also synthesized naphtho- and anthrodisilacyclobutadienes and compared their structure and (anti)aromaticity by various spectroscopies, structural analysis, and theoretical studies.
An isolable 1H-phosphadisilirene was obtained as red-purple crystalline solid. In obtained 1H-phosphadisilirene, significant orbital interactions between disilene moiety and phosphorus atoms in the three-membered ring was indicated by UV-vis spectrum and theoretical studies.

Research Products

• [Journal Article] A Series of Two-coordinate Group-15 Element (P, As, Sb, Bi) Centered Radicals Having Bulky Alkyl Groups (2018)
  • Author(s): Shintaro Ishida, Fumiya Hirakawa, Takeaki Iwamoto
  • Journal Title: Bull. Chem. Soc. Jpn. Volume: 91
  • NAID: 130007404810
  • Peer Reviewed
• [Journal Article] Synthesis and Functionalization of a 1,2-Bis(trimethylsilyl)-1,2-disilacyclohexene That Can Serve as a Unit of cis-1,2-Dialkyldisilene (2018)
  • Author(s): Naohiko Akasaka, Kaho Tanaka, Shintaro Ishida, Takeaki Iwamoto
  • Journal Title: Inorganics Volume: 6 Issue: 1 Pages: 21-21
  • DOI: 10.3390/inorganics6010021
  • Peer Reviewed / Open Access
• [Journal Article] Structural Change upon One-Electron Reduction of an Isolable Dialkylsilylene (2018)
  • Author(s): Takashi Abe, Shintaro Ishida, and Takeaki Iwamoto
  • Journal Title: Bulletin of Chemcal Society of Japan Volume: 91 Issue: 4 Pages: 684-686
  • DOI: 10.1246/bcsj.20170380
  • NAID: 130006707618
  • Peer Reviewed
• [Journal Article] Facile synthesis and bridgehead-functionalization of bicyclo[3.3.3]pentasiloxanes (2018)
  • Author(s): Yuki Yokouchi, Shintaro Ishida Shintaro, Tsunenobu Onodera, Hidetoshi, Takeaki Iwamoto
  • Journal Title: Chemical Communications Volume: 54 Issue: 3 Pages: 268-270
  • DOI: 10.1039/c7cc08790j
  • Peer Reviewed
• [Journal Article] Benzodisilacyclobutadienes: 8π-Electron Systems with an Antiaromatic Silicon Ring (2017)
  • Author(s): Ishida Shintaro、Misawa Yoshifumi、Sugawara Shohei、Iwamoto Takeaki
  • Journal Title: Angew.Chem. Int. Ed. Volume: 56 Issue: 44 Pages: 13829-13832
  • DOI: 10.1002/anie.201707553
  • Peer Reviewed
• [Journal Article] Heteroaryldisilenes: heteroaryl groups serve as electron acceptors for Si=Si double bonds in the intramolecular charge transfer transitions (2017)
  • Author(s): Tomoyuki Kosai, Shintaro Ishida, and Takeaki Iwamoto
  • Journal Title: Dalton Transactions Volume: 46 Issue: 34 Pages: 11271-11281
  • DOI: 10.1039/c7dt02357j
  • Peer Reviewed
• [Journal Article] A 1,2-Dibromosilene: Generation, Spectroscopic Observation and Isomerization to a Silacyclohexane via Facile 1,2-Bromine Shift (2017)
  • Author(s): Shintaro Ishida, Yushi Kato, Takeaki Iwamoto
  • Journal Title: Chem. Lett. Volume: 46 Issue: 8 Pages: 1155-1157
  • DOI: 10.1246/cl.170409
  • NAID: 130005907020
  • Peer Reviewed / Open Access
• [Journal Article] Coordination-induced Hydrogen Abstraction in the Reactions of a Stable Dialkylphosphinyl Radical with BH3-Lewis Base Adducts (2017)
  • Author(s): Shintaro Ishida, Hitomi Ichikawa, Takeaki Iwamoto
  • Journal Title: Chemistry Letters Volume: 46 Issue: 6 Pages: 883-885
  • DOI: 10.1246/cl.170248
  • NAID: 130005689312
  • Peer Reviewed
• [Journal Article] Isolation and Characterization of Radical Anions Derived from a Boryl-Substituted Diphosphene (2017)
  • Author(s): Asami, S.-s.; Ishida, S.; Iwamoto, T.; Suzuki, K.; Yamashita, M.
  • Journal Title: Angewandte Chemie International Edition Volume: 56 Issue: 6 Pages: 1658-1662
  • DOI: 10.1002/anie.201611762
  • NAID: 120006305576
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Pentasila-1,4-diene: Homoconjugation between Si=Si Double Bonds via a SiMe2 Unit (2017)
  • Author(s): Tomoyuki Kosai, Shintaro Ishida, Takeaki Iwamoto
  • Journal Title: J. Am. Chem. Soc. Volume: 139 Issue: 1 Pages: 99-102
  • DOI: 10.1021/jacs.6b11912
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] An Isolable Potassium Salt of a Borasilene - Chloride Adduct (2016)
  • Author(s): Suzuki, Y.; Ishida, S.; Sato, S.; Isobe, H.; Iwamoto, T.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 56 Issue: 16 Pages: 4593-4597
  • DOI: 10.1002/anie.201612545
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] A Potassium Diboryllithate: Synthesis, Bonding Properties, and the Deprotonation of Benzene (2016)
  • Author(s): Ohsato, T.; Okuno, Y.; Ishida, S.; Iwamoto, T.; Lee, K.-H.; Lin, Z.; Yamashita, M.; Nozaki, K.
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 38 Pages: 11426-11430
  • DOI: 10.1002/anie.201605005
  • Peer Reviewed / Int'l Joint Research / Acknowledgement Compliant
• [Journal Article] A Two-Coordinate Cyclic (Alkyl)(amino)silylene: Balancing Thermal Stability and Reactivity (2016)
  • Author(s): Tomoyuki Kosai, Shintaro Ishida, Takeaki Iwamoto
  • Journal Title: Angew. Chem. Int. Ed. Volume: 55 Issue: 50 Pages: 15554-15558
  • DOI: 10.1002/anie.201608736
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Recent Advances in η2-Disilene and η2-Disilyne Mononuclear Transition Metal Complexes and Related Compounds (2016)
  • Author(s): Shintaro Ishida, Takeaki Iwamoto
  • Journal Title: Coord. Chem. Rev. Volume: 314 Pages: 34-63
  • DOI: 10.1016/j.ccr.2015.11.007
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Hydrogen Bonds-Enabled Design of a C1-Symmetric Chiral Broensted Acid Catalyst (2016)
  • Author(s): Norie Momiyama, Kosuke Funayama, Hirofumi Noda, Masahiro Yamanaka, Naohiko Akasaka, Shintaro Ishida, Takeaki Iwamoto, and Masahiro Terada
  • Journal Title: ACS Catal. Volume: 6 Issue: 2 Pages: 949-956
  • DOI: 10.1021/acscatal.5b02079
  • Peer Reviewed
• [Journal Article] Ferrocenyl-substituted Bicyclo[1.1.1]pentasilanes: Evaluation of Significant Interactions between Ferrocenyl Units and Rigid Silicon Cages (2016)
  • Author(s): Yusuke Kishimoto, Shintaro Ishida, and Takeaki Iwamoto
  • Journal Title: Chem. Lett. Volume: 45 Issue: 2 Pages: 235-237
  • DOI: 10.1246/cl.151089
  • NAID: 130005124719
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Persistent four-coordinate iron-centered radical stabilized by π-donation (2016)
  • Author(s): Yusuke Sunada, Shintaro Ishida, Fumiya Hirakawa, Yoshihito Shiota, Kazunari Yoshizawa, Shinji Kanegawa, Osamu Sato, Hideo
  • Journal Title: Chem. Sci. Volume: 7 Issue: 1 Pages: 191-198
  • DOI: 10.1039/c5sc02601f
  • Peer Reviewed / Open Access
• [Journal Article] Persistent Dialkylsilanone Generated by Dehydrobromination of Dialkylbromosilanol (2015)
  • Author(s): Shintaro Ishida, Takashi Abe, Fumiya Hirakawa, Tomoyuki Kosai, Katsuhiro Sato, Mitsuo Kira, Takeaki Iwamoto
  • Journal Title: Chem. Eur. J. Volume: 21 Issue: 43 Pages: 15100-15103
  • DOI: 10.1002/chem.201501478
  • Peer Reviewed / Acknowledgement Compliant
• [Journal Article] Transformation of azulenes to bicyclic [4]dendralene and heptafulvene derivatives by photochemical cycloaddition of dialkylsilylene (2015)
  • Author(s): Tomoyuki Kosai, Shintaro Ishida, Takeaki Iwamoto
  • Journal Title: Chem. Commun. Volume: 51 Issue: 53 Pages: 10707-10709
  • DOI: 10.1039/c5cc03424h
  • Peer Reviewed / Acknowledgement Compliant
• [Presentation] Synthesis and Properties of Benzannelated Disilenes (2017)
  • Author(s): Shintaro Ishida, Yoshifumi Misawa, Shohei Sugawara, Takeaki Iwamoto
  • Organizer: The 18th International Symposium on Silicon Chemistry (ISOS-18)
  • Int'l Joint Research
• [Presentation] Generation and Spectroscopic Observation of Diorganosilanone in Solution (2017)
  • Author(s): Shintaro Ishida, Takashi Abe, Fumiya Hirakawa, Tomoyuki Kosai, Katsuhiro Sato, Mitsuo Kira, Takeaki Iwamoto
  • Organizer: International Symposium on Pure & Applied Chemistry 2017 (ISPAC2017)
  • Int'l Joint Research / Invited
• [Presentation] Generation of Diorganosilanone in the Condensed Phase (2016)
  • Author(s): Shintaro Ishida
  • Organizer: 8th European Silicon Days
  • Place of Presentation: Poznan, Poland
  • Year and Date: 2016-08-28
  • Int'l Joint Research
• [Presentation] 14族および15族元素の安定二配位化合物：分子デザイン、合成、特異な反応性 (2016)
  • Author(s): 石田真太郎
  • Organizer: 第49回有機金属若手の会夏の学校
  • Place of Presentation: 東海大学嬬恋高原研修センター, 群馬
  • Year and Date: 2016-07-12
  • Invited
• [Presentation] 低配位有機ケイ素および 有機リン化合物の安定化 (2016)
  • Author(s): 石田真太郎
  • Organizer: 第15回化学系若手研究者セミナー
  • Place of Presentation: 東北大学大学院薬学研究科 大講義室、宮城
  • Invited
• [Presentation] Synthesis, Properties, and Reactions of a Dialkyldisilyne (2015)
  • Author(s): Shintaro Ishida,Ryutaro Sugawara,Yoshifumi Misawa,Takeaki Iwamoto
  • Organizer: The 5th Asian Silicon Symposium
  • Place of Presentation: Lotte City Hotel Jeju, Jeju, Korea
  • Year and Date: 2015-10-18
  • Int'l Joint Research
• [Presentation] ２配位リン、アンチモン、ビスマス中心ラジカルの長寿命化による１５族化学の新展開 (2015)
  • Author(s): 石田真太郎
  • Organizer: 第３２回有機合成化学セミナー
  • Place of Presentation: ニューウェルシティ湯河原、神奈川
  • Year and Date: 2015-09-16
  • Invited
• [Presentation] Fascinating silicon-containing double bonds from silicon versions of carbene and alkyne (2015)
  • Author(s): 石田真太郎
  • Organizer: 平成27年度化学系学協会東北大会
  • Place of Presentation: 弘前大学文教キャンパス、弘前、青森
  • Year and Date: 2015-09-12
  • Invited
• [Presentation] Synthesis, Structure, and Properties of Stable Benzodisilacyclobutadienes (2015)
  • Author(s): Shintaro Ishida, Yoshifumi Misawa, Takeaki Iwamoto
  • Organizer: 第６２回有機金属化学討論会
  • Place of Presentation: 関西大学、吹田、大阪
  • Year and Date: 2015-09-07
• [Presentation] A stable disilyne having bulky alkyl groups and its palladium and platinum complexes (2015)
  • Author(s): Shintaro Ishida , Ryutaro Sugawara, Yoshifumi Misawa and Takeaki Iwamoto
  • Organizer: the 46th Silicon Symposium
  • Place of Presentation: University of California, Davis, USA
  • Year and Date: 2015-07-21
  • Int'l Joint Research
• [Book] Organosilicon Compounds: Theory and Experiment (Synthesis), Volume 1, L. Ya. Lee Ed., Chapter II.1.2.4, (2017)
  • Author(s): Takeaki Iwamoto, Shintaro Ishida
  • Total Pages: 171
  • Publisher: Elsevier
  • ISBN: 9780128019818