Interaction Between Ethynylsilanes and Transition-Metal-Complex

乙炔基硅烷与过渡金属络合物之间的相互作用

• 批准号: 01470096
• 负责人: ISHIKAWA Mitsuo
• 金额: $ 4.1万
• 依托单位: Hiroshima University
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for General Scientific Research (B)
• 财政年份: 1989
• 资助国家: 日本
• 起止时间: 1989 至 1990
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-01470096/
• 关键词: C-H Bond Activation; Organosilicon Polymer; エンイン; ジエン; シリルアセチレン; 触媒反応

1. We found that the reaction of ethynylsilanes with a catalytic amount of a rhodium (I) complex proceeds with remarkably regio-and stereospecificity to afford head-to-head coupling products, (E) -disilylenynes, as a single isomer in high yields. The silyl group on enynes thus obtained can be replaced by other organic groups. For example, treatment of the disilylenyne with 1 equiv of methyllithium gave a lithium acetylide quantitatively. Treatment of the disilylenyne with methanol in the presence of a catalytic amount of sodium methoxide gave a 1, 4-disilylbutadiene in high yield.2. Similar reaction of a diethynylsilane and diethynyldisilanes gave a poly [(silylene) butenyne-1, 4-diyl] and poly [(disilanylene) butenyne-1, 4-diyls], respectively. The polymers thus obtained were found to be photoactive. When the thin solid films prepared from the polymers were treated with SbF_5 vapor, highly conducting films were obtained whose conductivities were measured to be 0.0009-1.09 S/cm.3. We also investigated the nickel (0) -complex-catalyzed reaction of 2-aryl-substituted (phenylethynyl) trisilanes and found novel isomerization reactions via a silapropadiene-nickel complex formed presumably from a 1, 3-silyl shift to the ethynylic carbon atom.

1. 我们发现乙炔基硅烷与催化量的铑 (I) 络合物的反应具有显着的区域和立体特异性，以高产率提供单一异构体的头对头偶联产物 (E) -二甲硅烷基炔。由此获得的烯炔上的甲硅烷基可以被其他有机基团取代。例如，用1当量的甲基锂处理二甲硅烷基，定量地得到乙炔锂。在催化量的甲醇钠存在下，用甲醇处理二甲硅烷基，以高收率得到1,4-二甲硅烷基丁二烯。2．二乙炔基硅烷和二乙炔基二硅烷的类似反应分别产生聚[(亚硅基)丁烯炔-1, 4-二基]和聚[(二硅基)丁烯炔-1, 4-二基]。发现由此获得的聚合物具有光活性。当用SbF_5蒸气处理由聚合物制备的固体薄膜时，获得了高导电薄膜，其电导率测得为0.0009-1.09S/cm.3。我们还研究了镍 (0) 络合物催化的 2-芳基取代的（苯基乙炔基）三硅烷的反应，并发现了通过硅丙二烯-镍络合物进行的新型异构化反应，该络合物可能是由 1, 3-甲硅烷基转移到乙炔基碳原子形成的。

项目成果

Mitsuo Ishikawa: "SiliconーCarbon Unsaturated Compounds. XVII. NickelーCatalyzed Reactions of 2ーPhenylー, and 2ー(oーTol)ー2ー(phenylethynyl)hexamethyltrisilane" J.Organomet.Chem.399. 205-213 (1990)

石川光男：“硅－碳不饱和化合物。1990）

Joji Ohshita: "Polymeric Organosilicon Systems. 5. Synthesis of poly[(disilanylene)butenyne-1, 4-diyls] with Highly Conducting Properties" Organometallics. 8. 2084-2085 (1989)

Joji Ohshita：“聚合有机硅系统。5.具有高导电性能的聚[(二硅基)丁烯炔-1, 4-二基]的合成”有机金属。

Joji Ohshita: "Synthesis and Reactions of (E)ーBis(silyl)ーSubstituted Enynes" J.Org.Chem.55. 3277-3280 (1990)

Joji Ohshita：“(E)－双(甲硅烷基)－取代烯炔的合成和反应”J.Org.Chem.55 3277-3280 (1990)。

Joji, Ohshita: "Synthesis and Reactions of (E)-Bis(silyl)-Substituted Enynes" J. Org. Chem.55. 3277-3280 (1990)

Joji, Ohshita：“(E)-双(甲硅烷基)-取代烯炔的合成和反应”J. Org。

Mitsuo Ishikawa: "SiliconーCarbon Unsaturated Compounds.XVII.NickelーCatalyzed Reaction of 2ーPhenylー,and 2ー(oーTol)ー2ー(phenylethynyl)hexamethyltrisilane" J.Organomet.Chem.399. 205-213 (1990)

石川光男：“硅－碳不饱和化合物。1990）