ケイ素及びゲルマニウムを鍵元素とする高機能製分子の創出

1998 Fiscal Year Final Research Report Summary

• Project/Area Number: 08404042
• Research Category: Grant-in-Aid for Scientific Research (A)
• Allocation Type: Single-year Grants
• Section: 一般
• Research Field: Organic chemistry
• Research Institution: Tohoku University
• Principal Investigator: 吉良 満夫 東北大学, 大学院・理学研究所, 教授 (40004452)
• Co-Investigator(Kenkyū-buntansha): 坂本 健吉 東北大学, 大学院・理学研究所, 助教授 (50187035)
• Project Period (FY): 1996 – 1998
• Keywords: シクロトリシレン / シラトリアフルベン / ポリシラン / 安定シリレン / 非経験的分子軌道計算

Research Abstract

平成8年度から10年度までの3年間に、以下のような顕著な成果を挙げることができた。
1.環状不飽和ケイ素化合物の合成、構造と反応研究
(1)初めてのペルシラ環状不飽和化合物として、嵩高いトリアルキルシリル基で安定化されたヘキサキス(トリアルキルシリル)テトラシラシクロブテン(1)の合成に成功した。1と対応するテトラシラビシクロ[1.1.0〕プタン(2)間の速やかな異性化を見出し、その機構を明らかにした。
2)嵩高いトリアルキルシリル基で安定化された初めてのケイ素3員環2重結合分子としてテトラキス(トリアルキルシリル)シクロトリシレンを合成単離した。
(3)いくつかの非対称置換テトラシリルジシレンを合成単離し、ケイ素―ケイ素2重結合周りの回転障壁が著しく低いことを発見した。
(4)テトラシリルジシレンの種々の反応試剤との反応性を明らかにし、特にハロアルカンとの反応機構を詳しく研究し、ジシレンのラジカル反応性を明らかにした。
2.ケイ素―炭素2重結合を含む交差共役分子の合成、構造と反応研究
(1) 最小の含ケイ素交差共役π電子系である4-シラトリアフルベン誘導体の生成・単離に成功し、この系のケイ素―炭素2重結合はアルコールに対する付加反応性が著しく低いことを明らかにした。また、非経験的分子軌道計算によってモデル反応の遷移状態を明らかにした。
3.ジアミノシリレンの2量体を初めて実験的に観測した。理論的予測とは異なり、ケイ素―ケイ索2重結合ダイマーを生成することを確立した。
4.P-シアノフェニルペンタメチルジシランの超音速ジェット分光を行い、TICT型孤立分子として初めて分子として始めて分子内電化移動発光を見出した。
5.シロール環を連結したいくつかのオリゴ-1,1-シロールを合成し、紫外吸収スペクトルの系統的研究を行なった。

Research Products

• [Publications] T. Hoshi: "Synchronized fluorine exchange with ring inversion of pentafluro-1, 4-disila-cyclo-hexane anion"Chem. Lett.. 683-684 (1996)
• [Publications] M. Kira: "Tetrakis(trialkylsilyl) digermense. Salient effects of trialkylsilyl-substituents on planarity around Ge=Ge bond and remarkable thermochromism"Organometallics. 15. 3767-3769 (1996)
• [Publications] M. Kira: "The first stable cyclic disilene: hexakis(trialkylsilyl) tetrasilacyclobutene"J. Am. Chem. Soc.. 118. 10303-10304 (1996)
• [Publications] K. Ebihara: "Polysilane-based polymer diodes emitting ultraviolet light"Jpn. J. Appl. Phys.. 35. 1278-1280 (1996)
• [Publications] K. Ebihara: "Ultraviolet electroluminescence in polysilane thin film"J. Mol. Cryst. Liq. Cryst.. 286. 245-250 (1996)
• [Publications] M. Kira: "Synthesis and reactions of neutral hypercoordinate allylsilicon compounds having tropolonato ligand"Organometallics. 15. 5335-5341 (1996)
• [Publications] T. Miyazawa: "Action spectra of non-resonant two-photon (NRTO) isomerization of α, ω-diphenylpolyenes"Chem. Lett.. 1023-1024 (1996)
• [Publications] K. Skamoto: "Generation and trapping of bis (dialkylamino) silylenes: Experimental evidence for bridged structure of diaminosilylene dimers"Bull. Chem. Soc. Jpn.. 70. 253-260 (1997)
• [Publications] L. C. Zhang: "Enantioselective allylation of aldehydes using tartrate ester modified allylslanes"Chem. Lett.. 129-130 (1997)
• [Publications] M. Takahashi: "Atheoretical study of stereochesmistry of 1,3-migration in allylsilane and related allylmetallic compounds"J. Am. Chem. Soc.. 119. 1948-1953 (1997)
• [Publications] M. Kira: "Thermal ring-opening polymerization of [2.2] paracyclophanes having two disilanylenebridges"Organometallics. 16. 1100-1102 (1997)
• [Publications] K. Sakamoto: "The first silatriafulvene derivative: unusually low reactivity towards alcohols, and isomerization to silacyclobutadiene"J. Am. Chem. Soc.. 119. 3045-3406 (1997)
• [Publications] T. Miyazawa: "Selective carbon-bromine bond fission induced by non-resonant two-photon (NRTP) exciation of trans-4 bromostibene"Chem. Lett.. 459-460 (1997)
• [Publications] T. Miyazawa: "Remarkable suppression of [2+2] cycloaddition during non-resonant two-photon (NRTP) photoreaction of t-stilbene in the presence of tetramethylethylene"Photochm, Photobiol. 66. 566-568 (1997)
• [Publications] R. West: "A solid-state NMR and theoretical study of the chemical bonding in disilenes"J. Am. Chem. Soc.. 119. 4972-4976 (1997)
• [Publications] Y. Tajima: "First observation of intramolecular charge-transfer emission from jet-cooled (p-cyanophenyl)-pentamethyldisilane in an isolated molecular condition"J. Am. Chem. Soc.. 119. 7400-7401 (1997)
• [Publications] K. Ebihara: "Ultraviolet luminescence and electro-luminescence of poydihexylsilane"J. Lumin.. 72-74. 43-45 (1997)
• [Publications] K. Obata: "Induction of helical chirality in linear oligosilanes by terminal chiral substituents"J. Am. Chem. Soc.. 119. 11345-11346 (1997)
• [Publications] S. Tokura: "Novel σ-π alternating polymers having 2,2-biphridyl in the polymer backbone and their ruthenium complexes"Chem. Lett.. 1163-1164 (1997)
• [Publications] K. Sakamoto: "Preparation of hyperbranched polymethacrylates by self-condensing group transfer polymerization"Chem. Lett.. 1245-1246 (1997)
• [Publications] K. Kanno: "Synthesis and structure of a series of oligo [1,1-(2,3,4,5-tetramethylsilol)]s"Chem. Lett.. 99-100 (1998)
• [Publications] T. Miyazawa: "Photodegradation of polysilane polymers by non-resonant two-photon excitation"J. Am. Chem. Soc.. 120. 1084-1085 (1998)
• [Publications] K. Ebata: "Planar hexasilylbenzene dianion with thermally accessible triplet state"J. Am. Chem. Soc.. 120. 1335-1336 (1998)
• [Publications] T. Iwamoto: "A mechanistic study of thermal and photochemical isomerization between hexasilyltetttrasilabicyclo-[1.1.0] butane and hexasilyltetrasilacyclobutene"Chem. Lett.. 277-278 (1998)
• [Publications] M. Kira: "Structure of (Tropolonato)_4M-Type Compounds (M=Si, Ge, and Sn)"Organometallics. 17. 887-892 (1998)
• [Publications] T. Veszpremi: "An ab initio MO study of structure and reactivity of 4-silatriafulvene"J. Am. Chem. Soc.. 120. 2408-2414 (1998)
• [Publications] Y. Tajima: "Microscopic solvation effects on Si-Si bond cleavage reactions of cluster cation radicals of (p-cynophenyl) pentamethyldisilance with hydroxylic molecules"Chem. Lett.. 415-416 (1998)
• [Publications] K. Mochida: "Photochemical reactions of digermanyl-substituted naphthalenes: The germylmigration to the aromatic ring"J. Organomet. Chem.. 553. 163-171 (1998)
• [Publications] K. Obata: "Remarkable effects of side-chain alkyl substituents on thermochromic behaviour of peralkyldecasilanes"Chem. Commun.. 1309-1310 (1998)
• [Publications] K. Obata: "Temperature dependent CD spectra of poly (dihexylsilylene)s with terminal chiral groups. Coupled Cotton effects of silicon σ chains"Macromolecules. 31. 4666-4668 (1998)
• [Publications] S. Tsutsui: "X-Ray crystallographic analysis of a 3-silacyclopropene with electronegative substituents on silicon"Organometallics. 17. 3819-3821 (1998)
• [Publications] S. Tsutsui: "Bis(diisopropylamino)-silylene and its dimer"J. Am. Chem. Soc.. 120. 9955-9956 (1998)
• [Publications] M. Kira: "Persistent tri(t-butyldimethylsilyl) silyl radica and its new generation methods"Chem. Lett.. 1097-1098 (1998)
• [Publications] T. Iwamoto: "Bimolecular reactions of tetrakis(trialkylsilyl) disilenes with various reagents"Bull. Chem. Soc. Jpn.. 71. 2741-2747
• [Publications] T. Vszpremi: "Substiuent effects on the structure and aromaticity of 4-silatriafulvene"J. Phys. Chem. (A). 102. 10530-10535 (1998)
• [Publications] T. Iwamoto: "The first stable cyclotrisilene"J. Am. Chem. Soc.. 121(4). 886-887 (1999)
• [Publications] M. Kira: "Synthesis and structure of a stable cyclic dialkylgemylene"Chem. Lett.. 203-204 (1999)
• [Publications] L. C. Zhang: "Retention stereochemistry of thermal 1,3-silyl migration in allylic silanes"J. Am. Chem. Soc.. 121(12). 2925-3936 (1999)
• [Publications] T. Miyazawa: "Mechanistic studies of photochemical silylene extrusion from 2,2-diaryltrisilanes"J. Am. Chem. Soc.. 121(15). 3651-3656 (1999)
• [Publications] M. Kira: "The first isolable dialkylsilylene"J. Am. Chem. Soc.. (in press).
• [Publications] M. Takahashi: "Atheoretical study of mechanisms of 1,3-silyl migration in formylmethylsilane and related compounds. Comparison with allylsilane"J. Am. Chem. Soc.. (in press).
• [Publications] 宮澤貴士: "非線形工学応答を利用した光化学反応制御-非共鳴2光子励起法"応用物理. 66(7). 669-702 (1997)
• [Publications] M. Kira: "The Chemistry of Oganic Silicon Compounds"John-Wiley. 27 (1998)
• [Publications] 吉良満夫: "O plus E"株式会社新技術コミュニケーションズ. 6 (1998)