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Synthesis and Properties of New Silyl-Substituted pi-Electron Systems and Organosilicon Reactive Intermediates

Research Project

Project/Area Number 08404043
Research Category

Grant-in-Aid for Scientific Research (A)

Allocation TypeSingle-year Grants
Section一般
Research Field Organic chemistry
Research InstitutionScience University of Tokyo

Principal Investigator

SAKURAI Hideki  東京理科大学, 理工学部, 教授 (70025873)

Co-Investigator(Kenkyū-buntansha) SANJI Takanobu  東京理科大学, 総合研究所, 助手 (00287484)
Project Period (FY) 1996 – 1998
Project Status Completed (Fiscal Year 1998)
Budget Amount *help
¥33,200,000 (Direct Cost: ¥33,200,000)
Fiscal Year 1998: ¥3,100,000 (Direct Cost: ¥3,100,000)
Fiscal Year 1997: ¥3,200,000 (Direct Cost: ¥3,200,000)
Fiscal Year 1996: ¥26,900,000 (Direct Cost: ¥26,900,000)
Keywordspi-electron system / fulvene / radialene / trimethylenecyclopentene / anion / triplet / silylene / reactive intermediates / ジシレン / 速度論的パラメーター / 光反応 / 分子内反応 / 二量化 / 二価化学種 / 6パイ電子系 / 励起状態 / 二重結合 / 熱反応 / 捕捉生成物 / ケイ素置換パイ電子 / ジメチレンシクロブテン / ジアニオン / ジゲルメン
Research Abstract

Several new silyl-substituted pi-electron systems, such as fulvene, dimethylenecyclobutene, trimethylenecyclopentene, and [4]radialene, have been prepared by intramolecular polymerization of macrocyclic polyacetylenes. Two-electron reduction of these cyclic pi-systems with lithium creates interesting anionic species. Structures of the dianions of dimethylenecyclobutene, trimethylenecyclopentene, and [4]radialene are elucidated by X-ray crystallography. Interesting phenomena such as lithium-walk in the dianion of [4]radialene was observed.
The dianion of l, 3, 4, 6, 7, 9-hexasila-1, l, 3, 3, 4, 4, 6, 6, 7, 7, 9, 9-dodecamethyltriindane was planar and exhibited stable triplet esr spectrum at room temperature. Although the ground state was singlet but the singlet-triplet energy difference was only 1 kcal/mole that was the lowest value ever observed.
Several new reactive intermediates such as diamino-substituted silylenes, trimethylsilyl-methyl-substituted disilenes, and hexamethyltetrasila-1, 3-butadiene were generated and reaction modes were examined.

Report

(4 results)
  • 1998 Annual Research Report   Final Research Report Summary
  • 1997 Annual Research Report
  • 1996 Annual Research Report
  • Research Products

    (38 results)

All Other

All Publications (38 results)

  • [Publications] H.Sakura: "Novel π-electron systems derived from silicon-containing macrocyclic polyacetylenes" Pure Appl.Chem.68. 327-333 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ebata et al.: "Intramolecular oligomerization of disilalkylene {-Me_2Si(CH_2)_nSiMe_2-} bridged cyclic triacetylenes" Chem.Lett.1053-1054 (1996)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Sekiguchi et al.: "[1, 1, 2, 2-Tetrakis(dimethylsilyl)ethylene)]bis[(diethyl ether)lithium(I)] : Observation of an SiH-Li agostic interaction" Angew.Chem.Int.Ed.Engl.36. 1533-1535 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Sakamoto et al.: "Generation and trapping of bis(dialkylamino)silylenes : Experimental evidence for bridged structure of diaminosilvlene dimers" Bull.Chem.Soc.Jpn.70. 253-260 (1997)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ebata et al.: "Planar hexasilylbenzene dianion with thermally accessible triplet state" J.Am.Chem.Soc.120. 1335-1336 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Sekiguchi et al.: "Synthesis and characterization of the dilithium salt of the octasilyl[4]radialene dianion : Evidence for a lithium walk on the eight-center, ten-electron π-system" Angew.Chem., Int.Ed.37. 1662-1664 (1998)

    • Description
      「研究成果報告書概要(和文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Sakurai: "Novel pi-electron systems derived from silicon-containing macrocyclic polyacetylenes" Pure Appl.Chem.68. 327-333 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ebata, T.Matsuo, T.Inoue, Y.Otsuka, C.Kabuto, A.Sekiguchi, and H.Sakurai: "Intramolecular oligomerization of disilalkylene {-MeP_2Si(CH_2)_nSi Me_2-} bridged cyclic triacetylenes" Chem.Lett.1053-1054 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] M.Kira, T.Iwamoto, T.Maruyama, C.Kabuto, and H.Sakurai: "Tetrakis (trialkylsilyl) digermanes. Salient effects of trialkylsilyl substituents on planarity around the Ge=Ge bond and remarkable thermochromism" Organometallics. 15. 3767-3769 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Sekiguchi, T.Matsuo, K.Ebata, and H.Sakurai: "Persilylated dimethylenecyclobutane dianion dilithium as the first 6c-8pi allyl anion system" Chem.Lett.1133-1134 (1996)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Sakamoto, S.Tsutsui, H.Sakurai, and M.Kira: "Generation and trapping of bis (dialkylamino) silylenes : Experimental evidence for bridged structure of diaminosilylene dimers" Bull.Chem.Soc.Jpn.70. 253-260 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Sekiguchi, M.Nanjo, C.Kabuto, and H.Sakurai: "[Me(PhMe_2Si)_2SiLi] and [Ph(Me_3Si)_2SiLi] : Preparation, characterization, and evidence for an intramolecular Li-Ph interaction" Angew.Chem.Int.Ed.Engl.36. 113-115 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Sekiguchi, M.Ichinohe, M.Takahashi, C.Kabuto, and H.Sakurai: "[1,1,2,2-Tetrakis(dimethylsilyl)ethylene)]bis[(diethyl ether)lithium(I)] : Observation of an SiH-Li agostic interaction" Angew.Chem.Int.Ed.Engl.36. 1533 (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Sanji, T.Sakai, C.Kabuto, and H.Sakurai: "Silole incorporated polysilanes" J.Am.Chem.Soc.120. 4552-4553 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] H.Sakurai: "Anionic polymerization of masked disilenes to high molecular weight polysilanes : Mechanism, scope and applications, Macromolecular Design of Polymeric Materials, K.Hatada, T.Kitayama, and O.Vogl, eds." Marcel Dekker, Inc., New York. chapt.27. (1997)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] K.Ebata, W.Setaka, T.Inoue, C.Kabuto, M.Kira, and H.Sakurai: "Planar hexasilylbenzene dianion with thermally accessible triplet state" J.Am.Chem.Soc.120. 1335-1336 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Hoshi, R.Shimada, C.Kabuto, and H.Sakurai: "Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene" Chem.Lett.1998. 427-428

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Matsuo, A.Sekiguchi, M.Ichinohe, K.Ebata, and H.Sakurai: "Synthesis and reduction of octasily[4]radialene. Structure and dynamic study of [4]radialene dianion with eight-center ten-electron pi-system" Bull.Chem.Soc.Jpn.71. 1705-1711 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] A.Sekiguchi, T.Matsuo, and H.Sakurai: "Synthesis and characterization of the dilithium salt of the octasilyl[4]radialene dianion : Evidence for a lithium walk on the eight-center, ten-electron pi-system" Angew.Chem.Int.Ed.37. 1662-1664 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Matsuo, A.Sekiguchi, M.Ichinohe, K.Ebata, and H.Sakurai: "The first isolation and full characterization of fulvene dianion. Synthesis and X-ray structure of dilithium hexasilylfulvene dianion" Organometallics. 17. 3143-3145 (1998)

    • Description
      「研究成果報告書概要(欧文)」より
    • Related Report
      1998 Final Research Report Summary
  • [Publications] T.Sanji: "Highly Selective Mono- and Polyallyation of Polychlorosilanes and Disilanes" Organometallics. 17. 5068-5071 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Sanji: "Silole-Incorporated Polysilanes" J.Am.Chem.Soc.120. 4552-4553 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Hoshi: "Synthesis of Disilacycloalkenes by Ruthenium Catalyzed Ring-Closing Metathesis (RCM) Reaction of a, w-Bis(allydimethylsilyl)-Substituted Compounds" Bull.Chem.Soc.Jpn.72(in press). (1999)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Hoshi: "Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene" Chem.Lett. 427-428 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Iwamoto: "Bimolecular Reactions of Tetrakis(tr alkylsilyl)disilenes with Various Reagents" Bull.Chem.Soc.Jpn.71. 2741-2747 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] E.Ebata: "Planar Hexsasilylbenzene diaanion with thermally accessible triplet state" J.Am.Chem.Soc.120. 1335-1336 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] H.Sakurai: "The Chemistry of Organic Silicon Compounds" John Wiley & Sons Ltd, 28 (1998)

    • Related Report
      1998 Annual Research Report
  • [Publications] T.Sanji: "Anionic Ring Opening Polymerization of Octamethyltetrasilacyclopentane" Chem.Lett.1121-1122 (1997)

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Sanji: "Kinetics of Chain Organization at the Thermochromic Transition of Polysilanes" Chem.Lett.255-256 (1998)

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Sakurai: "Anionic Polymerization of Silicon-Containing Rings" Phosphorus,Sulfur,and Silicon. (in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] T.Hoshi: "Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene" Chem.Lett.(in press).

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Sakurai: "John Wiley & Sons" Mechanism and structures in alcohol addition reactions of disilenes and silenes (in press), 30

    • Related Report
      1997 Annual Research Report
  • [Publications] H.Sakurai: "Polymerization of in situ generated disilenese" J.Organomet.Chem.521. 286-293 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] H.Sakurai: "Novel π-electron systems derived from silicon-containing macrocyclic polyacetylenes" Pure Appl.Chem.68. 327-333 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] K.Ebata: "Intramolecular oligomerization of disilalkylene {-Me_2Si (CH_2)_n SiMe_<2->} bridged cyclic triacetylenes" Chem.Lett.1053-1054 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Kira: "Tetrakis (trialkylsilyl) digermanes. Salient effects of trialkylsilyl substituents on planarity around the Ge=Ge bond and remarkable thermochromism" Organometallics. 15. 3767-3769 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] A.Sekiguchi: "Persilylated dimethylenecyclobutane dianion dilithium as the first 6c-8π allyl anion sustem" Chem.Lett.1133-1134 (1996)

    • Related Report
      1996 Annual Research Report
  • [Publications] M.Kira: "Synthesis and reactions of neutral hypercoordinate allylsilicon compounds having a tropolonato ligand" Organometallics. 15. 5335-5341 (1996)

    • Related Report
      1996 Annual Research Report

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Published: 1996-04-01   Modified: 2016-04-21  

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