1990 Fiscal Year Annual Research Report

有機ケイ素および関連IVBカテネ-ト化合物の機能と物性

Research Project

Project/Area Number	02102004
Research Institution	Tohoku University
Principal Investigator	櫻井英樹東北大学, 理学部, 教授 (70025873)
Co-Investigator(Kenkyū-buntansha)	坂本健吉東北大学, 理学部, 助手 (50187035) 関口章東北大学, 理学部, 助教授 (90143164)
Keywords	有機ケイ素化合物 / アリルシラン / ベンゼンジアニオン / ポリシラン / アニオン重合 / 分子内電荷移動 / 光化学 / ab initio分子軌道法
Research Abstract	本研究課題では、以下の4つのテ-マについて研究を行った。主な結果を以下に述べる。 1.有機合成戦略としての有機ケイ素化合物の反応 5配位アリルシランは100%ジアステレオ選択性を示すなど、極めて有用な反応剤であることが分かった。この反応についてab initio分子軌道法を用いた詳細な理論計算を行い、その遷移状態や反応経路を解明した。 2.特異な構造を持つ有機ケイ素化合物および関連化合物の合成と物性水素をすべてトリメチルシリル基で置換したベンゼンを初めて合成し、その構造や物性を明らかにした。この化合物に代表されるシリルゼン類はリチウムによる2電子還元により容易にジアニオン種を与え、反芳香族など興味深い物性を示した。さらにシリルエチレン類のジアニオン種の構造や溶液中の挙動についても検討した。 3.新規有機ケシ素ポリマ-の開拓マスクされたジシレンのアニオン重合法により、置換基配列が高度に制御されたポリシランを初めて合成した。このポリマ-は顕著なサ-モクロミズムを示すなど、従来法で合成したものとは全く異なった物性を示した。またこの方法により、ポリシランと他のポリマ-とのブロック共重合体が容易に合成できることを示した。 4.有機ケイ素化合物の光化学 (1)光反応によりシラーmーキノメタンなど新規な有機ケイ素反応性中間体を合成し、その反応性を明らかにした。 (2)ポリシラン類の励起状態の挙動を蛍光分光法などを利用して詳細に検討し、σーπ電子系およびσーσ電子系においても分子内電荷移動が重要な役割を果すことを実証した。

Research Products
(16 results)

All Other

All Publications (16 results)

[Publications] A.Sekiguchi: "HighーPressure Synthesis,Structure,and Novel Photochemical Reactions of 7,7,8,8ーTeramethylー7,8ーdisilabicyclo[2.2.2]octaー2,5ーdiene" Chem.Commun.
[Publications] H.Sakurai: "Reduction of carbonーcarbon multiple bonds by a combination of hydrosilane and alcohol catalyzed by palladium.A convenient procedure to introduce deuterium" Main Group Met.Chem.
[Publications] H.Sakurai: "Recent advances in siliconーcontaining cyclic polyacetylenes" Heteroatom.Chem.
[Publications] A.Sekiguchi: "The first nonconjugated mononuclear benzene dianion.isolation and characterization of bis[(tetrahydrofuran)lithium(I)]hexakis(trimethylsilyl)Benzenide" J.Am.Chem.Soc.113. 1464-1465 (1991)
[Publications] K.Sakamoto: "Preparation and photochemistry of disilanylquinones:Formation of novel oxasilaーmーquinodimethane intermediates" J.Am.Chem.Soc.113. 1466-1468 (1991)
[Publications] M.Kira: "Regiospecific and diastereoselective crotylation of aldimines with crotyltrifluorosilanes activated by fluoride ion" Chem.Lett.277-280 (1991)
[Publications] M.Kira: "Conformational analysis of phenylpentamethyldisilane and related compounds as studied by free jet laser spectroscopy" Chem.Commun.
[Publications] M.Kira: "Stereochemistry and mechanism for the addition of alcohols to a cyclic silene" J.Am.Chem.Soc.
[Publications] A.Sekiguchi: "Solution structure of 1,2ーdilithio[tetrakis(trimethylsilyl)]ethane.Observation of σーand πーbonded 1,2ーdilithioethane and unexpected anionic rearrangement in THF" Organometallics.
[Publications] A.Sekiguchi: "Molecular structure of phenyl[tris(trimethylsilyl)]ethylene dilithium complex.An orthogonal dianion" J.Am.Chem.Soc.
[Publications] Y.Nakadaira: "Photoーinduced electron transfer reaction of polysilanes.Intramolecular trapping of a transient silyl radical cation with a nucleophile" Chem.Lett.327-330 (1991)
[Publications] M.Kira: "Ab initio MO study of the reaction of pentacoordinate allylsilicates with aldehydes" Chem.Let.387-390 (1991)
[Publications] K.Sakamoto: "Decamethylー1,4,5,8,11,12ーhexasilabicyclo[6.6.0]tetradecaー2,6,9,13ーtetrayne" Chem.Lett.
[Publications] M.Kira: "The first matrixーisolation and electronic structure of vinylーsubstituted silylenes" J.Am.Chem.Soc.
[Publications] Y.Nakadaira: "Mass spectral fragmentation of polysilanylakanols.The analogies between mass spectrometry and photoーinduced electron transfer" Chem.Lett.
[Publications] Y.Nakadaira: "Preparation and structure of silacycloheptatriene" Organometallics. 10. 435-442 (1991)

1990 Fiscal Year Annual Research Report

有機ケイ素および関連IVBカテネ-ト化合物の機能と物性

Principal Investigator

櫻井 英樹 東北大学, 理学部, 教授 (70025873)

Research Products

[Publications] A.Sekiguchi: "HighーPressure Synthesis,Structure,and Novel Photochemical Reactions of 7,7,8,8ーTeramethylー7,8ーdisilabicyclo[2.2.2]octaー2,5ーdiene" Chem.Commun.

[Publications] H.Sakurai: "Reduction of carbonーcarbon multiple bonds by a combination of hydrosilane and alcohol catalyzed by palladium.A convenient procedure to introduce deuterium" Main Group Met.Chem.

[Publications] H.Sakurai: "Recent advances in siliconーcontaining cyclic polyacetylenes" Heteroatom.Chem.

[Publications] A.Sekiguchi: "The first nonconjugated mononuclear benzene dianion.isolation and characterization of bis[(tetrahydrofuran)lithium(I)]hexakis(trimethylsilyl)Benzenide" J.Am.Chem.Soc.113. 1464-1465 (1991)

[Publications] K.Sakamoto: "Preparation and photochemistry of disilanylquinones:Formation of novel oxasilaーmーquinodimethane intermediates" J.Am.Chem.Soc.113. 1466-1468 (1991)

[Publications] M.Kira: "Regiospecific and diastereoselective crotylation of aldimines with crotyltrifluorosilanes activated by fluoride ion" Chem.Lett.277-280 (1991)

[Publications] M.Kira: "Conformational analysis of phenylpentamethyldisilane and related compounds as studied by free jet laser spectroscopy" Chem.Commun.

[Publications] M.Kira: "Stereochemistry and mechanism for the addition of alcohols to a cyclic silene" J.Am.Chem.Soc.

[Publications] A.Sekiguchi: "Solution structure of 1,2ーdilithio[tetrakis(trimethylsilyl)]ethane.Observation of σーand πーbonded 1,2ーdilithioethane and unexpected anionic rearrangement in THF" Organometallics.

[Publications] A.Sekiguchi: "Molecular structure of phenyl[tris(trimethylsilyl)]ethylene dilithium complex.An orthogonal dianion" J.Am.Chem.Soc.

[Publications] Y.Nakadaira: "Photoーinduced electron transfer reaction of polysilanes.Intramolecular trapping of a transient silyl radical cation with a nucleophile" Chem.Lett.327-330 (1991)

[Publications] M.Kira: "Ab initio MO study of the reaction of pentacoordinate allylsilicates with aldehydes" Chem.Let.387-390 (1991)

[Publications] K.Sakamoto: "Decamethylー1,4,5,8,11,12ーhexasilabicyclo[6.6.0]tetradecaー2,6,9,13ーtetrayne" Chem.Lett.

[Publications] M.Kira: "The first matrixーisolation and electronic structure of vinylーsubstituted silylenes" J.Am.Chem.Soc.

[Publications] Y.Nakadaira: "Mass spectral fragmentation of polysilanylakanols.The analogies between mass spectrometry and photoーinduced electron transfer" Chem.Lett.

[Publications] Y.Nakadaira: "Preparation and structure of silacycloheptatriene" Organometallics. 10. 435-442 (1991)

櫻井英樹東北大学, 理学部, 教授 (70025873)