2001 Fiscal Year Annual Research Report

高周期14族元素不飽和環状化合物の合成、構造および反応性

Research Project

Project/Area Number	12740338
Research Institution	University of Tsukuba
Principal Investigator	一戸雅聡筑波大学, 化学系, 講師 (90271858)
Keywords	高周期14族元素 / 有機ケイ素化合物 / 不飽和小員環化合物 / シリルカチオン / シリルラジカル / シリルアニオン / ケイ素π電子系化合物
Research Abstract	昨年度までに合成に成功している、フリーなケイ素カチオン種であり且つケイ素原子を骨格元素とするホモ芳香族性化学種であるシクロテトラシレニリウムイオンの1電子還元によりケイ素ラジカル種-シクロテトラシレニルラジカルが生成することを見い出し、ケイ素ラジカル種を初めて安定に単離することに成功した。X線結晶構造解析の結果、4員環内に組み込まれたアリル型ラジカルであることを明らかにし、シクロテトラシレニリウムイオンにおいて発現していた1,3_-位のケイ素間の相互作用によるホモ芳香族性が、1電子還元により消失することも分かった。また、シクロテトラシレニルラジカルのさらなる1電子還元によりケイ素4員環状アニオン種-シクロテトラシレニドイオンの合成にも成功し、その分子構造を決定した。本研究で合成、単離に成功したシクロテトラシレニリウムイオン-シクロテトラシレニルラジカル-シクロテトラシレニドイオンはそれぞれ反応活性なカチオン、ラジカル、アニオン中心がアリル型ケイ素π電子系上に非局在化していることを核磁気共鳴、電子スピン共鳴等の分光法により明らかにした。また、シクロテトラシレニリウムイオン-シクロテトラシレニルラジカル-シクロテトラシレニドイオンは化学的な酸化還元により相互変換が可能であり、高周期14族元素のみからなるπ電子系において2段階の可逆な酸化還元系を構築できることも明らかにした。

Research Products

(13 results)

All Other

All Publications (13 results)

[Publications] Mitsuo Kira: "A Mechanistic Study of Reactions of Stable Disilenes with Haloalkanes"Journal of the American Chemical Society. 123・8. 1676-1682 (2001)
[Publications] Akira Sekiguchi: "Cyclotetrasilenyl : The First Isolable Silyl Radical"Journal of the American Chemical Society. 123・49. 12436-12437 (2001)
[Publications] Fukaya Norihisa: "Ring Contraction of 1, 2-Digermacyclohexa-1, 4-diene to (Germacyclopent-3-enyl)germylene"Organometallics. 20・16. 3364-3366 (2001)
[Publications] Masaaki Ichinohe: "A New Approach to the Synthesis of Unsymmetrical Disilenes and Germasilene : Unusual ^<29>Si NMR Chemical Shifts and Methanol Addition with Unexpected Regiospecificity"Organometallics. 20・20. 4141-4143 (2001)
[Publications] Vladimir Ya. Lee: "Reaction of Disilagermirenes with Phenylacetylene : From a Germasilene -Ge=Si- to a Metalladiene of the Type -Si=Ge-C=C"Journal of Organometallic Chemistry. 636. 42-49 (2001)
[Publications] Vladimir Ya. Lee: "A New Pathway in the Reaction of Disilene with Carbonyl Compounds : an "Ene" Reaction instead of Cycloaddition"Chemical Communications. 20. 2146-2147 (2001)
[Publications] Vladimir Ya. Lee: "Reaction of 1-Disilagermirene with Benzaldehyde : An Unexpected Combination of Cycloaddition and Insertion Pathways"Chemistry Letters. 7. 728-729 (2001)
[Publications] Masaaki Ichinohe: "Photoisomerization of Persilyl-Substituted Silacyclopropene : Formation of Stable Persilyl-Substituted 1-Silaallene, and Its Reactivity"Chemistry Letters. 11. 1074-1075 (2001)
[Publications] Vladimir Ya. Lee: "Interconversion of Cyclotrimetallenes and Dihalocyclotrimetallanes Consisting of Group 14 Elements"Heteroatom Chemistry. 12・4. 223-226 (2001)
[Publications] Vladimir Ya. Lee: "Interaction of 1-Disilagermirene with Carbonyl Compounds"Main Group Metal Chemistry. 25・1. 1-4 (2002)
[Publications] Akira Sekiguchi: "The First Halogen-Substituted Cyclotrigermenes : A Unique Halogen Walk over the Three Membered Ring Skeleton and Facial Stereoselectivity in the Diels-Alder Reaction"Journal of the American Chemical Society. (印刷中). (2002)
[Publications] Tadahiro Matsuno: "Cyclotetrasilenide Ion : A Reversible Redox System of Cyclotetrasilenyl Cation, Radical, and Anion"Angewandte Chemie, International Edition. (印刷中). (2002)
[Publications] Akira Sekiguchi: "The First Isolable 1, 1-Dilithiogermane and its Unusual Dimeric Structure - a New Effective Reagent for the Preparation of Doubly-Bonded Derivatives of Group 14 Elements"Angewandte Chemie, International Edition. (印刷中). (2002)

2001 Fiscal Year Annual Research Report

高周期14族元素不飽和環状化合物の合成、構造および反応性

Principal Investigator

一戸 雅聡 筑波大学, 化学系, 講師 (90271858)

Research Products

[Publications] Mitsuo Kira: "A Mechanistic Study of Reactions of Stable Disilenes with Haloalkanes"Journal of the American Chemical Society. 123・8. 1676-1682 (2001)

[Publications] Akira Sekiguchi: "Cyclotetrasilenyl : The First Isolable Silyl Radical"Journal of the American Chemical Society. 123・49. 12436-12437 (2001)

[Publications] Fukaya Norihisa: "Ring Contraction of 1, 2-Digermacyclohexa-1, 4-diene to (Germacyclopent-3-enyl)germylene"Organometallics. 20・16. 3364-3366 (2001)

[Publications] Masaaki Ichinohe: "A New Approach to the Synthesis of Unsymmetrical Disilenes and Germasilene : Unusual ^<29>Si NMR Chemical Shifts and Methanol Addition with Unexpected Regiospecificity"Organometallics. 20・20. 4141-4143 (2001)

[Publications] Vladimir Ya. Lee: "Reaction of Disilagermirenes with Phenylacetylene : From a Germasilene -Ge=Si- to a Metalladiene of the Type -Si=Ge-C=C"Journal of Organometallic Chemistry. 636. 42-49 (2001)

[Publications] Vladimir Ya. Lee: "A New Pathway in the Reaction of Disilene with Carbonyl Compounds : an "Ene" Reaction instead of Cycloaddition"Chemical Communications. 20. 2146-2147 (2001)

[Publications] Vladimir Ya. Lee: "Reaction of 1-Disilagermirene with Benzaldehyde : An Unexpected Combination of Cycloaddition and Insertion Pathways"Chemistry Letters. 7. 728-729 (2001)

[Publications] Masaaki Ichinohe: "Photoisomerization of Persilyl-Substituted Silacyclopropene : Formation of Stable Persilyl-Substituted 1-Silaallene, and Its Reactivity"Chemistry Letters. 11. 1074-1075 (2001)

[Publications] Vladimir Ya. Lee: "Interconversion of Cyclotrimetallenes and Dihalocyclotrimetallanes Consisting of Group 14 Elements"Heteroatom Chemistry. 12・4. 223-226 (2001)

[Publications] Vladimir Ya. Lee: "Interaction of 1-Disilagermirene with Carbonyl Compounds"Main Group Metal Chemistry. 25・1. 1-4 (2002)

[Publications] Akira Sekiguchi: "The First Halogen-Substituted Cyclotrigermenes : A Unique Halogen Walk over the Three Membered Ring Skeleton and Facial Stereoselectivity in the Diels-Alder Reaction"Journal of the American Chemical Society. (印刷中). (2002)

[Publications] Tadahiro Matsuno: "Cyclotetrasilenide Ion : A Reversible Redox System of Cyclotetrasilenyl Cation, Radical, and Anion"Angewandte Chemie, International Edition. (印刷中). (2002)

[Publications] Akira Sekiguchi: "The First Isolable 1, 1-Dilithiogermane and its Unusual Dimeric Structure - a New Effective Reagent for the Preparation of Doubly-Bonded Derivatives of Group 14 Elements"Angewandte Chemie, International Edition. (印刷中). (2002)

一戸雅聡筑波大学, 化学系, 講師 (90271858)