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Imino(silyl)disilenes: application in versatile bond activation, reversible oxidation and thermal isomerization
Dalton Transactions ( IF 3.5 ) Pub Date : 2021-5-22 , DOI: 10.1039/d1dt01629f
Richard Holzner 1 , Amelie Porzelt 1 , Uhut S Karaca 2 , Fiona Kiefer 1 , Philipp Frisch 1 , Daniel Wendel 1 , Max C Holthausen 2 , Shigeyoshi Inoue 1
Dalton Transactions ( IF 3.5 ) Pub Date : 2021-5-22 , DOI: 10.1039/d1dt01629f
Richard Holzner 1 , Amelie Porzelt 1 , Uhut S Karaca 2 , Fiona Kiefer 1 , Philipp Frisch 1 , Daniel Wendel 1 , Max C Holthausen 2 , Shigeyoshi Inoue 1
Affiliation
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Two novel disilenes of type ABSi![[double bond, length as m-dash]](https://www.rsc.org/images/entities/char_e001.gif)
SiAB bearing N-heterocyclic imino (A = NItBu) and trialkylsilyl (B = SitBu3 1, B = SitBu2Me 2) groups are reported. The reduced steric demand in 2 results in a highly stable, nonetheless flexible system, wherefore (E/Z) isomerization is observed from room temperature up to 90 °C. The proposed isomerization mechanism proceeds via monomeric silylenes in line with experimental results. Despite enhanced stability, disilene 2 retains high reactivity in the activation of small molecules, including H2. The rare example of a disilene radical cation 7 is isolated and shows reversible redox behavior. White phosphorous (P4) selectively reacts with 2 to give the unique cage-compound 8. Selective thermal rearrangement of 2 at higher temperatures yields the A2SiSiB2-type disilene 9 (A = NItBu, B = SitBu2Me), which bears characteristics of a zwitterionic and a dative central Si–Si bond. The proposed mechanism proceeds via an initial NHI migration followed by silyl migration.
中文翻译：
亚氨基（甲硅烷基）二硅烷：在多功能键活化、可逆氧化和热异构化中的应用
报道了带有N-杂环亚氨基 (A = NI t Bu) 和三烷基甲硅烷基 (B = Si t Bu 3 1，B = Si t Bu 2 Me 2 ) 基团的两种新型 ABSi SiAB型二硅烯。在减小的空间需求2所导致高度稳定的，尽管如此灵活的系统，因此（ë / Ž）异构化从室温直至观察到90℃。所提出的异构化机制通过与实验结果一致的单体亚甲硅烷进行。尽管稳定性增强，二硅烯2在小分子（包括 H 2 ）的活化中保持高反应性。二硅烯自由基阳离子7的罕见例子是孤立的，并显示出可逆的氧化还原行为。白磷 (P 4 ) 选择性地与2反应生成独特的笼状化合物8。2在较高温度下的选择性热重排产生 A 2 Si SiB 2型二硅烯9（A = NI t Bu，B = Si t Bu 2 Me），其具有两性离子和配位中心 Si-Si 键的特性。拟议的机制通过 最初的 NHI 迁移，然后是甲硅烷基迁移。
更新日期：2021-06-04
SiAB bearing N-heterocyclic imino (A = NItBu) and trialkylsilyl (B = SitBu3 1, B = SitBu2Me 2) groups are reported. The reduced steric demand in 2 results in a highly stable, nonetheless flexible system, wherefore (E/Z) isomerization is observed from room temperature up to 90 °C. The proposed isomerization mechanism proceeds via monomeric silylenes in line with experimental results. Despite enhanced stability, disilene 2 retains high reactivity in the activation of small molecules, including H2. The rare example of a disilene radical cation 7 is isolated and shows reversible redox behavior. White phosphorous (P4) selectively reacts with 2 to give the unique cage-compound 8. Selective thermal rearrangement of 2 at higher temperatures yields the A2SiSiB2-type disilene 9 (A = NItBu, B = SitBu2Me), which bears characteristics of a zwitterionic and a dative central Si–Si bond. The proposed mechanism proceeds via an initial NHI migration followed by silyl migration.
中文翻译：
亚氨基（甲硅烷基）二硅烷：在多功能键活化、可逆氧化和热异构化中的应用
报道了带有N-杂环亚氨基 (A = NI t Bu) 和三烷基甲硅烷基 (B = Si t Bu 3 1，B = Si t Bu 2 Me 2 ) 基团的两种新型 ABSi SiAB型二硅烯。在减小的空间需求2所导致高度稳定的，尽管如此灵活的系统，因此（ë / Ž）异构化从室温直至观察到90℃。所提出的异构化机制通过与实验结果一致的单体亚甲硅烷进行。尽管稳定性增强，二硅烯2在小分子（包括 H 2 ）的活化中保持高反应性。二硅烯自由基阳离子7的罕见例子是孤立的，并显示出可逆的氧化还原行为。白磷 (P 4 ) 选择性地与2反应生成独特的笼状化合物8。2在较高温度下的选择性热重排产生 A 2 Si SiB 2型二硅烯9（A = NI t Bu，B = Si t Bu 2 Me），其具有两性离子和配位中心 Si-Si 键的特性。拟议的机制通过 最初的 NHI 迁移，然后是甲硅烷基迁移。
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