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Syntheses and Properties of Cyclopolysilanes with Well-defined Structures as Models for σ-Conjugation

Research Project

Project/Area Number 09304058
Research Category

Grant-in-Aid for Scientific Research (A).

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionGunma University

Principal Investigator

MATSUMOTO Hideyuki  Gunma University, Faculty of Engineering, Professor, 工学部, 教授 (90008467)

松本 英之 (2000)  群馬大学, 工学部, 教授 (40232384)

Project Period (FY) 1997 – 2000
Project Status Completed (Fiscal Year 2000)
Budget Amount *help
¥39,700,000 (Direct Cost: ¥39,700,000)
Fiscal Year 2000: ¥1,400,000 (Direct Cost: ¥1,400,000)
Fiscal Year 1999: ¥2,600,000 (Direct Cost: ¥2,600,000)
Fiscal Year 1998: ¥3,300,000 (Direct Cost: ¥3,300,000)
Fiscal Year 1997: ¥32,400,000 (Direct Cost: ¥32,400,000)
Keywordspolysilane / cyclopolysilane / ladder polysilane / σ-conjugation / molecular and crystal structures / chiral crystallization / ring-opening reaction / octagermacubane / 一電子還元 / キラル結晶化 / ラダーシロキサン / 過酸酸化 / 光反応 / シクロトリシラン / 臭素化 / 立体化学 / ジシラベンゾシクロブテン / 酸化 / シクロテトラシラン / セスキカルコゲニド / ダブルデッカー
Research Abstract

1. In a series of the anti isomers of the ladder polysilanes, the absorption maxima of the longest wavelength shift to the longer wavelength region as the number of cyclotetrasilane rings progressively increases. The shift is explained in terms of the stabilization of the lowest unoccupied molecular orbitals (LUMO) by the extension of the Si-Si σ-conjugation. The ladder polysilanes can be readily reduced by Na and K to generate the radical anions. The remarkable feature of the resulting radical anions is their unusual stability. For example, in the absence of dioxygen, the half-life of the pentacyclododecasilane is too long to be measured. The X-ray crystallography disclosed that the anti ladder polysilanes can be seen as silicon double helices, in which two linear polysilane chains screw in one way and are bridged by Si-Si bonds. Chiral symmetry breaking could be realized for anti-tricyclooctasilane. The crystallization gave one large crystal of each enantiomer M or P.The oxidation of … More the bicyclohexasilane with a deficient amount of m-chloroperbenzoic acid (MCPBA) resulted in the formation of 7-oxa compound, which shows stronger UV absorption and fluorescence. The domino oxidation predominates in the tri-, tetra-, and penta-oxidations of the tricyclooctasilane, tetracyclodecasilane, and pentacyclododecasilane with MCPBA, respectively.
2. From the stereochemical results observed in the ring-opening of the cis, cis- and cis, transcyclotrisilane [Ph (Thex) Si]_3 (Thex=1, 1, 2-trimethylpropyl) with halogens, it is concluded that the cleavage of the Si-Si bonds occurs with retention -inversion of the configuration of the Si atoms.
3. Octathexyloctagermacubane was synthesized to allow a comparison of chemical and physical properties of the alkyl-substituted octasilacubane with those of the corresponding octagermacubane. The octagermacubane is very stable to UV-Visible light, suggesting the unusual electronic and photochemical properties of the polyhedral germanium framework. Less

Report

(5 results)
  • 2000 Annual Research Report   Final Research Report Summary
  • 1999 Annual Research Report
  • 1998 Annual Research Report
  • 1997 Annual Research Report
  • Research Products

    (50 results)

All Other

All Publications (50 results)

  • [Publications] Masafumi Unno,Ryouji Tanaka,Toshie Kuribara,and Hideyuki Matsumoto: "Synthesis, Structures, and Reactions of 1,2,3-Tris (diethylamino)-1,2,3,4-tetrakis (1,1,2-trimethylpropyl) cyclotetrasilanes"Bull.Chem.Soc.Jpn,. 70. 2749-2756 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masafumi Unno,Yuuki Kawai,Hiroaki Shioyama,and Hideyuki Matsumoto: "Syntheses, Structures, and Properties of Tricyclo[5.1.1.1^<3,5>]tetrasila-chalcogenanes (Thex_2Si_2E_2)_2E_2 (E=S,Se) and Tricyclo[5.1.1.1^<3,5>]tetragermachalcogenanes (Thex_2Ge_2E_2)_2E_2(E=S,Se)"Organometallics. 16. 4423-4434 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masafumi Unno,Hiroyuki Masuda,and Hideyuki Matsumoto: "1,2,3-Triphenyl-1,2,3-trithexylcyclotrisilanes : Synthesis and Ring-Opening by Halogens"Bull.Chem.Soc.Jpn.. 71. 2449-2458 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Soichiro Kyushin,Tsukasa Kitahara,and Hideyuki Matsumoto: "Benzo [1,2:4,5] bis (1,1,2,2-tetraisopropyldisilacyclobeutene)"Chem.Lett.. 1998. 471-472 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Soichiro Kyushin,Haruaki Sakurai, and Hideyuki Matsumoto: "Highly Planar Silane (i-Pr)_3Si]_3SiH and Silyl Radial [(i-Pr)_3Si]_3Si・"Chem.Lett.,. 1998. 107-108 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Soichiro Kyushin,Ryoji Tanaka,Kuniaki Arai,,and Hideyuki Matsumoto: "Domino Oxidation of Ladder Oligosilanes : Formation of Novel Ladder Frameworks Containing Oligosiloxanes and Oligosilane Chains"Chem.Lett.,. 1999. 1297-1289 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masafumi Unno,Daisuke Ishii,and Hideyuki Matsumoto: "Kinetic Study of Thermal Isomerization of the "Double-decker" -type Sesqui- chalcogenides, (Thex_2M_2E_2)_2E_2 (M=Si, Ge; E=S, Se)"Bull.Chem.Soc.Jpn,. 72. 2469-2473 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoji Tanaka,Masafumi Unno,and Hideyuki Matsumoto: "Synthesis and Molecular Structures of Novel Isopropyl-substituted Oligosilanes.,"Chem.Lett. 1999. 595-596 (1999)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Sochioro Kyushin,Yo.Miyajima,and Hdieyuki Matsumoto: "Observation of Highly Stable Radical Anions of Ladder Oligosilanes"Chem.Lett.. 2000. 1420-1421 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masafumi.Unno,Koichi.Higuchi,and Hideyuki Matsumoto: "Synthesis, Structure, and Reactions of Octakis (1,1,2-trimethylpropyl)-octagermacubane,"Bull.Chem.Soc.Jpn.. 73. 2093-2097 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Soichiro Kyushin,Akira Meguro,and Hideyuki Matsumoto: "Photolysis of anti-Dodeca-isopropyltricyclo[4.2.0.0^<2,5>]octasilane : Generation and Reactions of Cyclotetrasilene,"Chem.Lett.,. 2000. 494-495 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hideyuki Matsumoto,Soichiro Kyushin,Masafunmi Unno,and Ryoji Tanaka: "Syntheses, Structures, and Properties of Ladder Oligosilanes and Ladder Oligogermanes"J.Organomet.Chem.. 611. 52-63 (2000)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masafumi Unno, Yuuki Kawai, Hiroaki Shioyama, and Hideyuki Matsumoto: "Syntheses, Structures, and Properties of Tricyclo [5.1.1.1^<3,5>]-tetrasil-chalcogenanes (Thex_2Si_2E_2)_2E_2 (E=S, Se) and Tricyclo [5.1.1.1^<3,5>] tetragermachalcogenanes (Thex_2Ge_2E_2)_2E_2 (E=S, Se)"Bull.Chem.Soc.Jpn.. 70. 2749-2756 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masafumi Unno, Hiroyuki Masuda, and Hideyuki Matsumoto: "1, 2, 3-Triphenyl-1, 2, 3-trithexylcyclotrisilanes : Synthesis and Ring-Opening by Halogens"Organometallics. 16. 4428-4434 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Soichiro Kyushin, Tsukasa Kitahara, and Hideyuki Matsumoto: "Benzo [1, 2 : 4, 5] bis (1, 1, 2, 2-tetraisopropyldisila-cyclobeutene)"Chem. Lett.. 471-472 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Soichiro Kyushin, Haruaki Sakurai, and Hideyuki Matsumoto: "Highly Planar Silane (i-Pr)_3Si]_3 SiH and Silyl Radial [(i-Pr)_3Si]_3Si"Chem.Lett.. 107-108 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Soichiro Kyushin, Ryoji Tanaka, Kuniaki Arai, and Hideyuki Matsumoto: "Domino Oxidation of Ladder Oligosilanes : Formation of Novel Ladder Frameworks Containing Oligosiloxanes and Oligosilane Chains"Chem.Lett.. 1297-1298 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masafumi Unno, Daisuke Ishii, and Hideyuki Matsumoto: "Kinetic Study of Thermal Isomerization of the "Double-decker"-type Sesquichalcogenides, (Thex_2M_2E_2)_2E_2 (M=Si, Ge ; E=S, Se)"Bull.Chem.Soc.Jpn.. 72. 2469-2473 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Ryoji Tanaka, Masafumi Unno, and Hideyuki Matsumoto: "Synthesis and Molecular Structures of Novel Isopropyl-substituted Oligosilanes"Chem.Lett.. 595-596 (1999)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Sochioro Kyushin, Yo.Miyajima, and Hdieyuki Matsumoto: "Observation of Highly Stable Radical Anions of Ladder Oligosilanes"Chem.Lett.. 1420-1421 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Masafumi.Unno, Koichi.Higuchi, and Hideyuki Matsumoto: "Synthesis, Structure, and Reactions of Octakis (1, 1, 2-trimethylpropyl) octagermacubane"Bull.Chem..Soc.Jpn.. 73. 2093-2097 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Soichiro Kyushin, Akira Meguro, and Hideyuki Matsumoto: "Photolysis of anti-Dodecaisopropyltricyclo [4.2.0.0^<2.5>]-octasilane : Generation and Reactions of Cyclotetrasilene"Chem.Lett.. 494-495 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] Hideyuki Matsumoto, Soichiro Kyushin, Masafunmi Unno, and Ryoji Tanaka: "Syntheses, Structures, and Properties of Ladder Oligosilanes and Ladder Oligogermanes"J.Organomet.Chem.. 611. 52-63 (2000)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      2000 Final Research Report Summary
  • [Publications] H.Matsumoto,S.Kyushin,M.Unno,and R.Tanaka: "Syntheses, Structures, and Properties of Ladder Oligosilanes and Ladder Oligogermanes"J.Organomet.Chem.. 611. 52-63 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Kyushin,Y.Miyajima,and H.Matsumoto: "Observation of Highly Stable Radical Anions of Ladder Oligosilanes"Chem.Lett.. 1420-1421 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] S.Kyushin,A.Meguro,M.Unno,and H.Matsumoto: "Photolysis of anti-Dodecaalkyltricyclo [4.2.0.0^<2,5>] octasilane : Generation and Reactions of Cyclotetrasilene"Chem.Lett.. 494-495 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Unno,K.Higuchi,K.Furuya,H.Shioyama,S.Kyushin,M.Goto,and H.Matsumoto: "Synthesis, Structure, and Reactions of Octakis (1, 1, 2-trimethylpropyl) octagermacubane"Bull.Chem.Soc.Jpn.. 73. 2093-2097 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] H.Horiuchi,Y.Nakano,T.Matsumoto,M.Unno,H.Matsumoto,and H.Hiratsuka: "Electronic Structure and Photochemical Reaction Intermediates of Octakis (1, 1, 2-trimethylpropyl) octasilacubane"Chem.Phys.Lett.. 322. 33-40 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Unno,K.Takada,and H.Matsumoto: "Formation of Supermolecule by Assembling of Two Different Silanols"Chem.Let.t. 242-243 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Unno,A.Suto,K.Takada,and H.Matsumoto: "Synthesis of Ladder and Cage Silsesquioxanes from 1,2,3,4-Tetraydroxycycloterasiloxane"Bull.Chem.Soc.Jpn.. 73. 215-220 (2000)

    • Related Report
      2000 Annual Research Report
  • [Publications] M.Unno,K.Negishi,and H.Matsumoto: "Extended Silapericyclynes"Chem.Lett.. 340-341 (2001)

    • Related Report
      2000 Annual Research Report
  • [Publications] Soichiro Kyushin: "Phtotolysis of anti-Dodecaalkyltricyclo[4.2.0.0^<2,5>]octasilane:Generation and Reactions of Cyclotetrasilene"Chem.Lett.. (印刷中). (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Masafumi Unno: "Synthesis of Ladder and Cage Silsesquioxanes from 1,2,3,4-Tetrahydroxycyclo-tetrasiloxane"Bull.Chem Soc.Jpn.. 73巻. 215-220 (2000)

    • Related Report
      1999 Annual Research Report
  • [Publications] Soichiro Kyushin: "Domino Oxidation of Ladder Oligosilanes:Formation of Novel Ladder Frameworks Containing Oligo-siloxanes and Oligosilane Chains"Chem.Lett.. 12号. 1297-1298 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Masafumi Unno: "Thermal Isomerization of Silicon and Germanium Sesquichalcogenides,(Thex_2M_2E_2)_2E_2(M=Si,Ge;E=S,Se)"Bull.Chem Soc.Jpn.. 72巻. 2460-2473 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Ryoji Tanaka: "Synthesis and Molecular Structures of Novel Isopropyl-substituted Oligosilanes"Chem.Lett.. 7号. 595-596 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Masafumi Unno: "Synthesis and Characterization of Cage and Bicyclic Silsesquioxanes via Dehydration of Silanols"Appl.Organomet.Chem.. 13巻. 303-310 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Masafumi Unno: "Synthesis and Reactions of Hepta-t-butylcyclotetragermane"Phosphorus,Sulfur and Silicon. 150-151巻. 167-176 (1999)

    • Related Report
      1999 Annual Research Report
  • [Publications] Soichiro Kyushin: "Highly Planar[(i-Pr)_3Si]_3SiH and Silyl Radical[(i-Pr)_3Si]_3Si" Chem.Lett.2号. 107-108 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Soichiro Kyushin: "Benzo[1,2:4,5]bis(1,1,2,2,-tetraisopropyldisilacyclobutene)" Chem.Lett.6号. 471-472 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Masafumi Unno: "Synthesis,Structure,and Reaction of the Tetrahydroxycyclotetrasiloxane,[(i-Pr)(OH)SiO]_4" Chem.Lett.6号. 489-490 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Masafumi Unno: "1,2,3-Triphenyl-1,2,3-trithexylcyclotrisilanes:Synthesis and Ring-Opning by Halogens" Bull.Chem.Soc.Jpn.71巻10号. 2449-2458 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Mitsuo Kira: "Persistent Tris(t-butyldimethylsiltl)silyl Radical and Its New Generation Methods" Chem.Lett.11号. 1097-1098 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] Masafumi Unno: "Synthesis and Characterization of Cage and Bicyclic Silsesquixanes Via dehydration Of Silnols" Appl.Organomatal.Chem.(掲載予定). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] Masafumi Unno: "Synthesis and structures,and Reactions of 1,2,3-Tris (diethylamino) -1,2,3,4- tetrakis (1,1,2-trimethylpropyl) cyclotetrasilanes" Bull.Chem.Soc.Japan. 70. 2749-2756 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Masafumi Unno: "Syntheses,Structures,and Properties of Tricyclo [5.1.1^<3.5>] tetrasilachalcogenanes (Thex_2Si_2E_2) E_2 (E=S,Se) and Tricyclo [5.1.1^<3.5>] tetrasilachalcogenanes (Thex_2Si_2E_2) E_2 (E=S,Se) (E=S,Se)" Organometallics. 16. 4428-4434 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Soichiro Kyushin: "Highly Stable Silyl Radicals (Et_nMe_<3-n>Si)_3Si (n=1-3)" Organometallics. 16. 5386-5388 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] Soichiro Kyushin: "Highly Plannar Silane [(i-Pr)_3Si]_3SiHSiH and Silyl Radical [(i-Pr)_3Si]" Chem.Lett.2号. 107-108 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Masafumi Unno: "Synthesis,Structure,and Reaction of the Tetrahydrocyclotetrasiloxane [(i-Pr)(OH)SiO]_4" Chem.Lett. 掲載決定. (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] Masafumi Unno: "Synthesis and Characterization of Cage and Bicyclic Silsesquioxanes via Dehydration of Silanols" Appl.Organomet.Chem.掲載決定. (1998)

    • Related Report
      1997 Annual Research Report

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Published: 1997-04-01   Modified: 2016-04-21  

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