ケイ素三重結合化合物を鍵モノマーとするポリアセチレンケイ素類縁体の創製

使用硅三键化合物作为关键单体创建聚乙炔硅类似物

• 批准号: 17655014
• 负责人: 関口 章
• 金额: $ 2.05万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Exploratory Research
• 财政年份: 2005
• 资助国家: 日本
• 起止时间: 2005 至 2007
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-17655014/
• 关键词: 高周期典型元素; ケイ素-ケイ素三重結合; ケイ素ポリマー; π電子系ポリマー; ジシリン; ジシレニルリチウム; 環化付加; ジシラベンゼン; 重合反応; 高周期14族元素; 高周期14族元素三重結合

ケイ素などの第3周期以降の高周期典型元素におけるπ電子系化合物(多重結合化合物)は炭素などの第2周期元素π電子系化合物に比べ、占有π軌道準位が著しく高く、非占有π*軌道準位が著しく低いという特徴を持つ。またケイ素-ケイ素σ結合(単結合)の軌道準位は炭素-炭素π軌道準位に匹敵するほど高く、ケイ素-ケイ素単結合で連なったポリマー(ポリシラン)では主鎖を形成するσ電子が、炭素π共役系におけるπ電子のように非局在化するσ共役を発現することも知られている。従って、ポリアセチレンのケイ素類縁体であるポリジシリンでは、高周期元素特有の非局在化したσ電子によるσ共役に加えてπ共役の複合化による新規な物性発現も期待される。本研究では、筆者らが初めて安定な化合物として合成・単離することに成功したケイ素-ケイ素三重結合化合物(ジシリン)の反応性を検討してきた。有機リチウム開始剤によるアニオン重合を行うべく、種々の有機リチウム試剤との反応を行ったところ、tert-ブチルリチウムでは1電子移動とそれに引き続く水素移動を経て、水素置換ジシレニルリチウム種を与え、単独重合は進行しなかった。また、ジシリンの重合活性の向上を目指して新規な置換基を導入したモノマー(ジシリン)の合成検討を行った。その結果、ジアルキル(アリール)シリル基を導入したジシリンは、spケイ素が空間的に接近するアリール基に対して反応活性であり、spケイ素が空間的に接近するアリールC-H結合へ挿入を経て異性化するため、ジシリン自体を安定に単離することが出来なかった。一方、トリアルキルシリル基を導入した第2のジシリンを安定に合成することには成功し、その分子構造を単結晶X線結晶構造解析で決定した。

During the third cycle of the cycle, the typical elements of the high cycle, the π electron compounds (multiple compounds), the carbon compounds, the second cycle elements, the π electron compounds, the π channel alignment, the high temperature, the non-occupation, the low temperature, the high temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the high temperature, the low temperature, the low temperature, the high temperature, the low temperature, the high temperature, the high temperature, the low temperature, the high temperature, the low temperature The alignment of carbon-carbon π channel alignment is consistent with that of carbon-carbon π channel alignment. The carbon-carbon π channel alignment is similar to the carbon-carbon π channel alignment, and the carbon π co-operation system is used to realize that the carbon π electrons and carbon π co-operation systems are not in the local chemisty. the carbon π co-operation system and the carbon π co-service system are used to realize that the carbon π electrons are not in the local system. In general, high-cycle elements are unique to the general system and the characteristics of high-cycle elements. in addition to the combination of σ-electron and π-co-service, it is expected that new rules of physical properties can be realized. In this study, the compound of diazepam was synthesized successfully. The triple compound (compound) of antidiazepam and diazepam was successfully synthesized. There are two types of equipment that can be used to prevent the transfer of water and water. All kinds of equipment will be used to carry out the operation of the same kind of equipment. There are two kinds of equipment, one kind of equipment, one type of equipment, one, two, two, one, two, one, two, two, one, two, two, one, one, two, two, one, two, two, one, one, two, one, one, two, one, two The coincident activity is up and down. The new rules are used to set the base to synthesize the new rules. The results of the experiment, the results of the test, the data base of the test data, the temperature close to the temperature response of the customer in the space of the sp, the temperature in the space of the sp, and the temperature of the customer in the space of the sp were combined with those of the customer, and the self-stability of the system was isolated. On the one hand, the molecular structure was introduced into the second phase. The synthesis of diazepam was successful, and the molecular structure of the crystal X-ray was analyzed.

项目成果

Conversion of a Si=Si Double Bond Into a Si=C Double Bond: Synthesis and Characterization of Silyl Anion-substituted Silene and Cyclic Silene from the Reaction of sp^2-Type Silyl Anion

Si=Si 双键转化为 Si=C 双键：sp^2 型硅阴离子反应生成硅阴离子取代的硅烯和环状硅烯的合成与表征

• 发表时间: 2007
• 作者: H.Hotta;T.Ishijima;M.Sato;H.Sugai;菅井 秀郎(分担執筆);A. Sekiguchi;R. Kinjo;S. Inoue;I. Bejan;R. Kinjo;Gernot Frenking;Norio Nakata;Norio Nakata;Norio Nakata et al.;Norio Nakata et al.;Bagrat A.Shainyan et al.;A. Sekiguchi;S. Inoue
• 通讯作者: S. Inoue

Conversion of a Disilenide into a Silene: Silyl-Anion-Substituted Silene by Sila-Peterson-Type Reaction from an sp^2-Type Silyl Anion

将二硅烯化物转化为硅烯：通过 sp^2 型硅基阴离子的 Sila-Peterson 型反应将硅基阴离子取代的硅烯

• 发表时间: 2007
• 期刊: Angew. Chem, Int. Ed. 46
• 作者: T. Yamao;K. Yamamoto;Y. Taniguchi;*S. Hotta;K. Akagi;M. Goh;Z. X. Jin;M. Goh;M. Kyotani;P. Kuad;T. Ogoshi;N. Sugiyama;T. Fujii;S. Inoue
• 通讯作者: S. Inoue

Utility of sp^2-Type Silyl Anion: Synthesis and Structure of Hydrosilene and Boryl-substituted Disilene

sp^2型硅基阴离子的用途：氢硅烯和硼基取代二硅烯的合成与结构

• 发表时间: 2007
• 作者: H.Hotta;T.Ishijima;M.Sato;H.Sugai;菅井 秀郎(分担執筆);A. Sekiguchi;R. Kinjo;S. Inoue;I. Bejan;R. Kinjo;Gernot Frenking;Norio Nakata;Norio Nakata;Norio Nakata et al.;Norio Nakata et al.;Bagrat A.Shainyan et al.;A. Sekiguchi;S. Inoue;A. Sekiguchi;A. Sekiguchi;井上 茂義;S. Inoue
• 通讯作者: S. Inoue

A stable Schrock-type hafnium-silylene complex

• DOI: 10.1021/ja067251d
• 发表时间: 2006-12-20
• 期刊: JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
• 影响因子: 15
• 作者: Nakata, Norio;Fujita, Toshiyuki;Sekiguchi, Akira
• 通讯作者: Sekiguchi, Akira

Computational study of tetrasilylcyclobutadiene dianion and its dilithium salt. 6e–6c Three-dimensional aromaticity

• DOI: 10.1016/j.theochem.2005.02.041
• 发表时间: 2005-09
• 期刊: Journal of Molecular Structure-theochem
• 作者: B. Shainyan;A. Sekiguchi