Construction of Novel Silicon? Silicon Double-bond Compounds Bearing Alkynyl Substituents

2011 Fiscal Year Final Research Report

• Project/Area Number: 21750042
• Research Category: Grant-in-Aid for Young Scientists (B)
• Allocation Type: Single-year Grants
• Research Field: Organic chemistry
• Research Institution: Kyoto University
• Principal Investigator: MIZUHATA Yoshiyuki 京都大学, 化学研究所, 助教 (30437264)
• Project Period (FY): 2009 – 2011
• Keywords: 有機元素化学 / 典型元素 / ケイ素 / π拡張分子 / 芳香族化合物

Research Abstract

We successfully accomplished the synthesis, isolation and characterization of 1, 2-dialkynyldislenes containing various substituents. A closer investigation of their spectroscopic properties clearly showed a conjugation ofπ-electrons between the disilene and alkynyl moieties. Desilylation or degermylation reactions of trimethylsilylethynyl or trimethylgermylethynyl-substituted disilenes with methyllithium resulted in the formation of the corresponding lithium acetylide derivatives, which were subsequently protonated to yield 1, 2-dialkynyldislenes with terminal alkynyl groups. These disilenes are potentially useful synthons for the construction of novelπ-conjugated systems containing disilene units

Research Products

• [Journal Article] Evidence for a LiBr-Assisted Generation of a Silylene from a1, 2-Diaryl-1, 2-dibromodisilene (2012)
  • Author(s): Han, J. S.; Sasamori, T.; Mizuhata, Y.; Tokitoh, N
  • Journal Title: Chem. Asian J Volume: 7 Pages: 298-300
  • DOI: DOI:10.1002/asia.201100833
  • Peer Reviewed
• [Journal Article] Reactions of an Overcrowded Silylene with Pyridines : Formation of a Novel 2H-1, 2-Azasilepine and Its Further Cycloaddition (2012)
  • Author(s): Mizuhata, Y.; Sato, T.; Tokitoh, N
  • Journal Title: Heterocycles Volume: 84 Pages: 413-418
  • DOI: DOI:10.3987/com-11-s(p)89
  • Peer Reviewed
• [Journal Article] New Aspects in the Coordination Chemistry of Ge-and Sn-Containing Metallaaromatic Compounds (2011)
  • Author(s): Tokitoh, N.; Inamura, K.; Mizuhata, Y
  • Journal Title: Phosphorus Sulfur and Silicon and the Related Elements Volume: 186 Pages: 1323-1325
  • DOI: DOI:10.1080/10426507.2010.543113
  • Peer Reviewed
• [Journal Article] 含高周期14族元素芳香族化合物の化学 (2011)
  • Author(s): 水畑吉行・時任宣博
  • Journal Title: 有機合成化学協会誌 Volume: 69 Pages: 691-704
  • DOI: DOI:10.5059/yukigoseikyokaishi.69.691
  • Peer Reviewed
• [Journal Article] The First Observation of^1J(Sn-C) Coupling Constants in Tin-arbon Double-bond Compounds (2010)
  • Author(s): Mizuhata, Y.; Tokitoh, N
  • Journal Title: Appl. Organ met. Chem Volume: 24 Pages: 902-906
  • DOI: DOI:10.1002/aoc.1741
  • Peer Reviewed
• [Journal Article] Generation of Stannabenzenes and Their Properties (2010)
  • Author(s): Mizuhata, Y.; Noda, N.; Tokitoh, N
  • Journal Title: Organometallics Volume: 29 Pages: 4871-4784
  • DOI: DOI:10.1021/om100382n
  • Peer Reviewed
• [Journal Article] Reactivity of an aryl-substituted silicon. silicon triple bond : 1, 2-Disilabenzenes from the reactions of a1, 2-diaryldisilyne with alkynes (2010)
  • Author(s): Han, J. S.; Sasamori, T.; Mizuhata, Y.; Tokitoh, N
  • Journal Title: Dalton Trans Volume: 39 Pages: 9238-9240
  • DOI: DOI:10.1039/C0DT00115E
  • Peer Reviewed
• [Journal Article] 1, 2-Dialkynyldisilenes : Silicon analogues of(E)-enediyne (2010)
  • Author(s): Sato, T.; Mizuhata, Y.; Tokitoh, N.
  • Journal Title: Chem. Commun Volume: 46 Pages: 4402-4404
  • DOI: DOI:10.1039/C0CC00406E
  • Peer Reviewed
• [Journal Article] Novel Silacyclohexadienyl Chromium and Iron Complexes Bearing a Bulky Substituenton the Central Silicon Atom (2010)
  • Author(s): Tanabe, Y.; Mizuhata, Y.; Tokitoh, N.
  • Journal Title: Pure Appl. Chem Volume: 82 Pages: 879-890
  • DOI: DOI:10.1351/PAC-CON-09-10-08
  • Peer Reviewed
• [Journal Article] Reactivity of an Aryl-Substituted Silicon亡ilicon Triple Bond : Reactions of a 1, 2-Diaryldisilyne with Alkenes (2010)
  • Author(s): Han, J. S.; Sasamori, T.; Mizuhata, Y.; Tokitoh, N
  • Journal Title: J. Am. Chem. Soc Volume: 132 Pages: 2546-2547
  • DOI: DOI:10.1021/ja9108566
  • Peer Reviewed
• [Journal Article] Synthesis and Structure of a Heavier Congener of Biphenyl : 1, 1'-Disila-4, 4'-biphenyl (2010)
  • Author(s): Tanabe, Y.; Mizuhata, Y.; Tokitoh, N.
  • Journal Title: Organometallics Volume: 29 Pages: 721-723
  • DOI: DOI:10.1021/om901095w
  • Peer Reviewed
• [Journal Article] Cycloaddition Reactions of Kinetically Stabilized 9-Silaanthrancenewith Polycyclic Aromatic Hydrocarbons (2009)
  • Author(s): Mizuhata, Y.; Shinohara, A.; Tanabe, Y.; Tokitoh, N
  • Journal Title: Chem. Eur. J Volume: 15 Pages: 8405-8408
  • DOI: DOI:10.1002/chem.200901290
  • Peer Reviewed
• [Journal Article] Stable heavier carbene analogues (2009)
  • Author(s): Mizuhata, Y.; Sasamori, T.; Tokitoh, N
  • Journal Title: Chem. Rev Volume: 109 Pages: 3479-3511
  • DOI: DOI:10.1021/cr900093s
  • Peer Reviewed
• [Journal Article] Reactions of a Kinetically Stabilized 2-Stannanaphthalenewith Elemental Sulfur and Selenium : Synthesis of Novel Cyclic Chalcogenides Containing a Tin Atom (2009)
  • Author(s): Mizuhata, Y.; Tokitoh, N
  • Journal Title: J. Sulf. Chem Volume: 30 Pages: 385-392
  • DOI: DOI:10.1080/17415990903033368
  • Peer Reviewed
• [Journal Article] Reaction of 9-Germaphenanthrene with Dimethyl Acetylenedicarboxylate : Unexpected Formation of a 1, 2-Oxagermolane Derivative (2009)
  • Author(s): Mizuhata, Y.; Inamura, K.; Tokitoh, N
  • Journal Title: Heterocycles Volume: 77 Pages: 811-816
  • DOI: DOI:10.3987/COM-08-S(F)82
  • Peer Reviewed
• [Journal Article] Syntheses and structures of overcrowded silanedichalcogenols and their applications to the syntheses of silanedichalcogenolato complexes (2009)
  • Author(s): Tanabe, T.; Mizuhata, Y.; Takeda, N.; Tokitoh, N
  • Journal Title: J. Organ met. Chem Volume: 694 Pages: 353-365
  • DOI: DOI:10.1016/j.jorganchem.2008.11.001
  • Peer Reviewed
• [Presentation] Reactive Intermediates and Unusual Molecules-A Celebration of Bob Moss's 70 Years (2012)
  • Author(s): Tokitoh, N.; Han, J. S.; Hironaka, K.; Sasamori, T.; Mizuhata, Y.
  • Organizer: International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2012-12-17
• [Presentation] Synthesis and Properties of Novel Extendedπ-Conjugated Systems of Heavier Main Group Elements (2010)
  • Author(s): Tokitoh, N.; Tanabe, Y.; Sato, T.; Mizuhata, Y
  • Organizer: International Chemical Congress of Pacific Basin Societies
  • Place of Presentation: Honolulu, USA
  • Year and Date: 2010-12-18
• [Presentation] New Reactivity of a 1, 2-Diaryldisilyne, the First Carbon-substituted Disilyne (2010)
  • Author(s): Tokitoh, N.; Han, J. S.; Hironaka, K.; Sugiyama, Y.; Mizuhata, Y, ; Sasamori, T.
  • Organizer: Japan-Taiwan Joint Symposium on Innovative Synthesis for New Materials Chemistry
  • Place of Presentation: Uji, Japan
  • Year and Date: 2010-10-05
• [Presentation] New Aspects in the Coordination Chemistry of Ge-and Sn-Containing Metallaaromatic Compounds (2010)
  • Author(s): Tokitoh, N.; Inamura, K.; Mizuhata, Y
  • Organizer: The 13th International Conference on the Coordination and Organ metallic Chemistry of Germanium Tin and Lead
  • Place of Presentation: Graz, Austria
  • Year and Date: 2010-07-13
• [Presentation] 含高周期14族元素芳香族化合物.遷移金属錯体の合成とその性質 (2009)
  • Author(s): 水畑吉行・稲村晃司・田邊祐介・時任宣博
  • Organizer: 第59回錯体化学討論会
  • Place of Presentation: 長崎大学
  • Year and Date: 2009-09-25
• [Presentation] Some New Reactions of a Kinetically Stabilized Silabenzene and Isolation of a Stable 1, 1'-Disila-4, 4'-biphenyl (2009)
  • Author(s): Tokitoh, N.; Tanabe, Y.; Mizuhata, Y
  • Organizer: The 13th International Symposium on Novel Aromatic Compounds
  • Place of Presentation: Luxembourg
  • Year and Date: 2009-07-22
• [Remarks]
  • URL: http://boc.kuicr.kyoto-u.ac.jp/.mizu/