Synthesis of Stable Silyl Radicals and Their Application to Multi-spin System

稳定硅基自由基的合成及其在多自旋系统中的应用

• 批准号: 14340192
• 负责人: MATSUMOTO Hideyuki
• 金额: $ 6.78万
• 依托单位: Gunma University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (B)
• 财政年份: 2002
• 资助国家: 日本
• 起止时间: 2002 至 2004
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-14340192/
• 关键词: Silyl Radical; Silyl Anion; Cyclopolysilane; Ladder Polysilane; Polycyclopolysilane; シリルビラジカル; シアニオン; 開殻化学種; ラジカル; 安定ラジカル; ポリシラン; ラダーポリシロキサン; アニオンラジカル

The following results have been obtained on the stabilization, syntheses, and structures and silyl radicals and the related open-shell species.1)The reduction of bromo[tris(triisopropylsilyl)]silane with alkali metals led to the formation of [tris(triisopropylsilyl)]silyl radical, which was isolated as yellow crystals. The molecular and crystal structure of the silyl radical were determined by X-ray crystallography. It was found that the formation of the stable silyl radical can be carried out in the preparative-scale experiment. The study on the magnetic properties of the silyl radical is underway.2)trans-1,2,2,3,4,4-Hexa-tert-buy1-1,3-cyclotetrasilanediyl)potassium, which represents the first example of cyclic silyl dianion, was synthesized by the reaction of trans-1,2,2,3,4,4-hexa-tert-buy1-1,3-dibromocyclotetrasilane with potassium in benzene. The X-ray crystallographic analysis of the compound-benzene complex showed a novel supramolecular structure, in which the compound and benzene are stacked alternatively to form an infinite 1-D structure.3)The silyl-centered biradical, 1,2,2,3,4,4-hexa-tert-buy1-1,3-cyclotetrasilanediyl), was formed as red crystals by the reduction of trans-1,2,2,3,4,4-hexa-tert-buy1-1,3-dibromocyclotetrasilane with potassium in benzene. Studies on the X-ray structure determination and magnetic properties of the crystalline biradical were underway.

在稳定化、合成、结构、硅自由基及相关开壳层物种等方面取得了如下结果：1）溴代[三（三异丙基硅基）]硅烷经碱金属还原生成[三（三异丙基硅基）]硅自由基，分离得到黄色晶体。通过X射线晶体学测定了硅自由基的分子和晶体结构。结果表明，稳定的硅自由基的形成可以在小规模实验中进行。2）以反式-1，2，2，3，4，4-六叔丁基-1，3-二溴环四硅烷为原料，在苯中与钾反应，合成了第一例环硅负离子反式-1，2，2，3，4，4-六叔丁基-1，3-环四硅烷二基）钾。3）通过反式-1，2，2，3，4，4-六叔丁基-1，3-环四硅烷二基的还原反应，得到了以硅烷基为中心的双自由基1，2，2，3，4，4-六叔丁基-1，3-环四硅烷二基（1，2，2，3，4，4-hexa-tert-bu 1 - 1，3-cyclotetrasilanidyl）的红色晶体。3-二溴环四硅烷与钾的苯溶液。晶体双自由基的X射线结构测定和磁性研究正在进行中。

项目成果

Stereoisomers of 1,3,5,7-Tetrahydroxy-1,3,5,7-tetaisopropylcyclotetrasiloxane : Synthesis and Structures in the Crystal

1,3,5,7-四羟基-1,3,5,7-四异丙基环四硅氧烷的立体异构体：合成和晶体结构

• 发表时间: 2005
• 期刊: J.Am.Chem.Soc. 127
• 作者: Masafumi Unno;Hideyuki Matsumoto
• 通讯作者: Hideyuki Matsumoto

Oligocyclic Laddersiloxanes : Alternative Synthesis by Oxidation

寡环梯硅氧烷：氧化替代合成

• 发表时间: 2005
• 期刊: Organometallics 24
• 作者: Masafumi Unno;Hideyuki Matsumoto
• 通讯作者: Hideyuki Matsumoto

(trans- 1,2,2,3,4,4-Hexa-tert-butyl-1,3-cyclotetrasilanediyl)potassium : Supra-molecular Structure of Silylpotassium-Benzene Complex

(反式1,2,2,3,4,4-六叔丁基-1,3-环四硅烷二基)钾：甲硅烷基钾-苯配合物的超分子结构

• 发表时间: 2004
• 期刊: Organometallics 23
• 作者: Soichiro Kyushin;Hiroko Kawai;Hideyuki Matsumoto
• 通讯作者: Hideyuki Matsumoto

Bicyclic and Tricyclic Ladder Compounds Consisting of Two Oligosiloxane Chains Bridged by Si-Si Rungs

由 Si-Si 横档桥接的两条低聚硅氧烷链组成的双环和三环梯状化合物

• 发表时间: 2004
• 期刊: Chemistry Letters 33
• 作者: Soichiro Kyushin;Hideyuki Matsumoto
• 通讯作者: Hideyuki Matsumoto

Stereoisomers of 1,3,5,7i-Tetrahydroxy-1,3,5,7-tetaisopropylcyclotetrasiloxane : Synthesis and Structures in the Crystal

1,3,5,7i-四羟基-1,3,5,7-四异丙基环四硅氧烷的立体异构体：合成和晶体结构

• 发表时间: 2005
• 期刊: Journal of the American Chemical Society 127
• 作者: Masafumi Unno;Yasuaki Kawaguchi;Yukiko Kishimoto;Hideyuki.Matsumoto
• 通讯作者: Hideyuki.Matsumoto