Versatile Synthesis of Sila-and Germa-(Dewa-benzene) and Their Valence Isomerization

Sila-和Germa-（Dewa-苯）的多功能合成及其化合价异构化

• 批准号: 16550027
• 负责人: KABE Yoshio
• 金额: $ 2.18万
• 依托单位: Kanagawa Univerity
• 依托单位国家: 日本
• 项目类别: Grant-in-Aid for Scientific Research (C)
• 财政年份: 2004
• 资助国家: 日本
• 起止时间: 2004 至 2005
• 项目状态: 已结题
• 来源: https://kaken.nii.ac.jp/en/grant/KAKENHI-PROJECT-16550027/
• 关键词: Sila-aromatics; silabenzeneValence Isomer; 1,4-disila(Dewar-benzene); disilabenzvalene; 1,4-disilabenzene; 原子価異性体; 1,4ジシラデュワーベンゼン; 1,4-ジシラベンゼン錯体; ジシラプリズマン

As versatile and high-yield synthetic method of 1,4-disila(Dewar-benzene), it has been found that reductive coupling of 1,4-dichlorocyclohexadiene, which was prepared by silylation of teterachlorocyclohexadiene following Jung's report.The photolysis of 1,4-disila(Dewar-benzene) afforded to give disilabenzvalene. Low-temperature photolysis in matrix (3-MP) disclosed 1,4-disilabenzene as a transient, intermediate. The reduction of 1,4-disila(Dewar-benzene) yielded dianion species. In order to gernerate 1,4-disilabenzene, oxidation of dianion species with BrCH2CH2Br met with failure.Toward the isolation of 1,4-disilabenzene as a stable metal complex, photochemical reaction of 1,4-disila(Dewar-benzene) with metal carbonyls were cried out. As a result, CO insertion into Si-Si bond of 1,4-disial(Dewar-benzene) was occurred. Without metal carbolyls, photochemical reaction under CO gas also gave the same product.Another synthetic attempts, more smaller substituents such as methyl and tolyl groups on Si atoms were tried to introduce without success.Theoretical calculations on the 1,4-disila(Dewar-benzene) and its's valence isomerization have been done. Several transition structures disclosed a unique reaction pathways on 1,4-disilabenzene valence isomerization.

作为1,4-二甲硅（脱瓦尔苯）的多功能和高收益合成方法，已经发现，1,4-二氯环己二烯的还原性偶联是通过teterachlorocyclohensene的报告来制备的。 DiSilabenzvalene。基质（3-MP）中的低温光解揭示了1,4-二甲苯苯作为瞬态，中间体。减少1,4-二甲硅（脱瓦尔）产生了dianion物种。为了使1,4-二甲苯苯乙烯与BRCH2CH2BR失败的氧化物质氧化。TOWARD将1,4-二甲苯苯二异苯乙烯分离为稳定的金属络合物，将1,4-二甲硅（Dewar-苯苯）的光化学反应与金属羰基分离出来。结果，发生CO插入1,4-二苯键（脱瓦尔苯）的Si-Si键。在没有金属核苷的情况下，Co气体下的光化学反应也给出了相同的产品。其他合成尝试，试图引入更多较小的取代基，例如Si原子上的甲基和甲甲基基团，而无需成功地引入。对1,4-二甲基（Dewar-benzene）的理论计算，以及其价值异构化。几个过渡结构在1,4-二甲苯苯偶发异构化上揭示了独特的反应途径。

项目成果

Silylium Ions Stabilization by an Si-Si Three-Center Bond(X=Halogen or Hydorogen)

通过 Si-Si 三中心键稳定硅离子（X=卤素或氢）

• 发表时间: 2004
• 期刊: Chem Lett 33
• 作者: A Sekiguti;Y Murakami;N Fukaya;Y kabe
• 通讯作者: Y kabe

Silyl-Substituted 1,4-Disila(Dewar benzene) : New Synthesis and Unexpected Insertion of CO into the Si-Si Bond Form a Disilyl Ketone

甲硅烷基取代的 1,4-Disila（杜瓦苯）：新合成以及 CO 意外插入 Si-Si 键形成二甲硅烷基酮

• 发表时间: 2005
• 期刊: Organometallics 24
• 作者: N.Nakata;T.Oikawa;T.Matsumoto;Y.Kabe;A.Sekiguchi
• 通讯作者: A.Sekiguchi

Silyl-Substituted 1,4-Disila(Dewar benzene) : New Synthesis and Unexpected Insertion of CO into the Si-Si Bond To Form a Disily Ketone

甲硅烷基取代的 1,4-Disila（杜瓦苯）：新合成以及意外地将 CO 插入 Si-Si 键中形成二甲硅烷基酮

• 发表时间: 2005
• 期刊: Organometallics 24
• 作者: N.Nakata;T.Oikawa;T.Matsumoto;A.Sekuguchi;Y.Kabe
• 通讯作者: Y.Kabe

Sylylium Ions Stabilized by an Si-X-Si Three-Center Bond (X=Halogen or Hydrogen

由 Si-X-Si 三中心键稳定的 Sylylium 离子（X=卤素或氢）

• 发表时间: 2004
• 期刊: Chem.Lett. 33
• 作者: A.Sekuguchi;Y.Murakami;N.Fukaya;Y.Kabe
• 通讯作者: Y.Kabe

Silyl-Substituted 1,4/Disila(Dewar benzene) : New Synthesis Disilyl Ketone

甲硅烷基取代的 1,4/Disila(杜瓦苯)：新合成二甲硅烷基酮

• 发表时间: 2005
• 期刊: Organometallics 24
• 作者: N Nakata;T Oikawa;Matsumoto;Y Kabe;A Sekiguchi
• 通讯作者: A Sekiguchi