Synthesis and Properties of New Silyl-Substituted pi-Electron Systems and Organosilicon Reactive Intermediates

新型甲硅烷基取代π电子体系及有机硅反应中间体的合成及性能

• 批准号: 08404043
• 负责人: SAKURAI Hideki
• 金额: $ 21.25万
• 依托单位: Science University of Tokyo
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (A)
• 财政年份: 1996
• 资助国家: 日本
• 起止时间: 1996 至 1998
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/grant/KAKENHI-PROJECT-08404043/
• 关键词: pi-electron system; fulvene; radialene; trimethylenecyclopentene; anion; triplet; silylene; reactive intermediates; ジシレン; 速度論的パラメーター; 光反応; 分子内反応; 二量化; 二価化学種; 6パイ電子系; 励起状態; 二重結合; 熱反応; 捕捉生成物; ケイ素置換パイ電子; ジメチレンシクロブテン; ジアニオン; ジゲルメン

Several new silyl-substituted pi-electron systems, such as fulvene, dimethylenecyclobutene, trimethylenecyclopentene, and [4]radialene, have been prepared by intramolecular polymerization of macrocyclic polyacetylenes. Two-electron reduction of these cyclic pi-systems with lithium creates interesting anionic species. Structures of the dianions of dimethylenecyclobutene, trimethylenecyclopentene, and [4]radialene are elucidated by X-ray crystallography. Interesting phenomena such as lithium-walk in the dianion of [4]radialene was observed.The dianion of l, 3, 4, 6, 7, 9-hexasila-1, l, 3, 3, 4, 4, 6, 6, 7, 7, 9, 9-dodecamethyltriindane was planar and exhibited stable triplet esr spectrum at room temperature. Although the ground state was singlet but the singlet-triplet energy difference was only 1 kcal/mole that was the lowest value ever observed.Several new reactive intermediates such as diamino-substituted silylenes, trimethylsilyl-methyl-substituted disilenes, and hexamethyltetrasila-1, 3-butadiene were generated and reaction modes were examined.

通过大环聚乙炔的分子内聚合，合成了富烯、二甲基环丁烯、三亚甲基环戊烯和[4]放射烯等几种新的硅基取代聚电子体系。这些环状pi体系与锂的两电子还原反应产生了有趣的阴离子物种。二甲基环丁烯、三亚甲基环戊烯和[4]放射烯的双阴离子的结构通过X-射线结晶学进行了鉴定。L，3，4，6，7，9-六硅杂-1，L，3，3，4，4，4，6，6，7，7，9，9-十二烷基三丹的二阴离子是平面的，在室温下表现出稳定的三重态ESR谱。虽然基态为单重态，但单重态-三重态的能量差仅为1千卡/摩尔，是迄今观察到的最低值。生成了几种新的反应中间体，如二氨基取代硅烯、三甲基硅甲基取代二硅烯和六甲基四硅烷-1，3-丁二烯，并对反应模式进行了考察。

项目成果

K.Sakamoto et al.: "Generation and trapping of bis(dialkylamino)silylenes : Experimental evidence for bridged structure of diaminosilvlene dimers" Bull.Chem.Soc.Jpn.70. 253-260 (1997)

K.Sakamoto 等人：“双（二烷基氨基）硅烯的生成和捕获：二氨基硅烯二聚体桥接结构的实验证据”Bull.Chem.Soc.Jpn.70。

T.Hoshi, R.Shimada, C.Kabuto, and H.Sakurai: "Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene" Chem.Lett.1998. 427-428

T.Hoshi、R.Shimada、C.Kabuto 和 H.Sakurai：“三甲基甲硅烷基甲基取代的掩蔽二硅烯的分子结构和光化学反应”Chem.Lett.1998。

A.Sekiguchi, T.Matsuo, and H.Sakurai: "Synthesis and characterization of the dilithium salt of the octasilyl[4]radialene dianion : Evidence for a lithium walk on the eight-center, ten-electron pi-system" Angew.Chem.Int.Ed.37. 1662-1664 (1998)

A.Sekiguchi、T.Matsuo 和 H.Sakurai：“八硅基[4]放射烯二阴离子的二锂盐的合成和表征：锂在八中心、十电子 pi 系统上行走的证据”Angew。

T.Hoshi: "Molecular Structure and Photochemical Reactions of Trimethylsilylmethyl-Substituted Masked Disilene" Chem.Lett. 427-428 (1998)

T.Hoshi：“三甲基甲硅烷基甲基取代的掩蔽二硅烯的分子结构和光化学反应”Chem.Lett。

T.Sanji: "Anionic Ring Opening Polymerization of Octamethyltetrasilacyclopentane" Chem.Lett.1121-1122 (1997)

T.Sanji：“八甲基四硅环戊烷的阴离子开环聚合”Chem.Lett.1121-1122 (1997)