Synthesis and reactions of polythiadisilabicyclo [k.l.m] alkanes having Unusual Bond-Order

具有异常键序的聚硫二硅双环[k.l.m]烷烃的合成与反应

• 批准号: 05453061
• 负责人: ANDO Wataru
• 金额: $ 4.61万
• 依托单位: University of Tsukuba
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1993
• 资助国家: 日本
• 起止时间: 1993 至 1995
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-05453061/
• 关键词: Silicon; Sulfur; Bicyclo [k.l.m] alkanes; Polysulfide; 立体圧縮効果; [1.1.1]プロペラン; ビシクロ[k.l.m]アルカン; ポリスルフィド; ポリセレニド; ジシラビシクロ[k.l.m]アルカン; ジゲルマビシクロ[k.l.m]アルカン; ビシクロ[1.1.1]ペンタン; トリチアジシラビシクロ[1.1.1]ペンタン; ヘキサチアジシラビシクロ[3.2.1]オクタン; ジシラビシクロ[1.1.1]ペンタン

The reaction of tris (trimethylsilyl) methylsilane (TsiSiH_3) with elemental sulfur afforded 1,3-bis {tris (trimethylsilyl) methyl}-2,4,5,6,7,8-hexathia-1,3-disilabicyclo [3.2.1] octane (6), 1,3-bis {tris (trimethylsilyl) methyl}-2,4,5,6,7-pentathia-1,3-disilabicyclo [2.1.1] heptane (b5), and 1,3-bis {tris (trimethysilyl) methyl}-2,4,5,6-tetrathia-1,3-disilabicyclo [2.1.1] hexane (4)in 12%, 12%, and 22% yields respectively. Structures of these compounds were confirmed by X-ray diffraction analysis. 1,3-Bis {tris (trimethylsilyl) methyl}-2,4,5-trithia [1.1.1] pentane (3) was obtained by photolysis of 4 in the presence of trimethylphosphine, quantitatively. The distance between the bridgehead silicon atoms of 2.407 A in 3 lies in the range of common Si-Si single bonds.

三(三甲基硅基)甲基硅烷(TsiSiH_3)与元素硫反应得到1,3-双{三(三甲基硅基)甲基}-2,4,5,6,7,8-六硫基-1,3-二硅双环[3.2.1]辛烷(6),1,3-双{三(三甲基硅基)甲基}-2,4,5,6,7,8-六硫基-1,3-二硅双环[3.2.1]辛烷(6) 甲基}-2,4,5,6,7-五硫基-1,3-二硅双环[2.1.1]庚烷(b5)和1,3-双{三(三甲基甲硅烷基)甲基}-2,4,5,6-四硫基-1,3-二硅双环[2.1.1]己烷(4)，产率分别为12%、12%和22%。这些化合物的结构通过X射线衍射分析得到证实。在三甲基膦存在下通过光解4定量获得1,3-双{三(三甲基甲硅烷基)甲基}-2,4,5-三硫[1.1.1]戊烷(3)。桥头硅原子之间的距离为2.407 A in 3 ，处于常见的Si-Si单键范围内。

项目成果

N.Choi,W.Ando: "Synthesis and Reactions of a Metallathiacyclopentanone" Organometallics. 13. 741-743 (1994)

N.Choi，W.Ando：“金属硫杂环戊酮的合成和反应”有机金属化合物。

W.Ando, S.Watanabe, N.Choi: "Synthesis and Structure of 1,3-Bis [tris (trimethylsilyl)-nethyl]-2,4,5-triselena-1,3-digermabicyclo [1.1.1] pentane" J.Chem.Soc.Chem.Comun.1683-1694 (1995)

W.Ando、S.Watanabe、N.Choi：“1,3-双[三(三甲基硅基)-甲基]-2,4,5-triselena-1,3-二甲双环[1.1.1]戊烷的合成和结构

W. Ando, S. Watanabe, N. Choi: "Synthesis and Structure of 1, 3-Bis [tris(trimethylsilyl)methyl]-2, 4, 5-triselena-1, 3-digermabicyclo[1. 1. 1] pentane" J. Chem. Soc., Chem. Commun.1683-1684 (1995)

W. Ando、S. Watanabe、N. Choi：“1, 3-双[三(三甲基硅基)甲基]-2, 4, 5-triselena-1, 3-digermabicyclo[1. 1. 1] 的合成和结构

W.Ando, S.Watanabe, N.Choi: "Synthesis and Structure of 1,3-Bis[tris(trimethylsilyl)-methyl]-2,4,5-triselena-1,3-digermabicyclo[1.1.1]pentane" J.Chem.Soc.,Chem.Comun.1683-1684 (1995)

W.Ando、S.Watanabe、N.Choi：“1,3-双[三(三甲基甲硅烷基)-甲基]-2,4,5-triselena-1,3-二甲双环[1.1.1]戊烷的合成和结构

Nami Choi: "Synthesis and Reactions of Metallathiacyclopentanone Complex" Organometallics. 13. 741-743 (1994)

Nami Choi：“Metallathiacyclopentanone 配合物的合成和反应”有机金属化合物。