4.8 Article

Unusual Reactivity of a Disilyne with 4-Dimethylaminopyridine: Formation of an Intramolecularly N-Coordinated Silylene and Its Isomerization to a Zwitterionic Silyl Anion

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JOURNAL OF THE AMERICAN CHEMICAL SOCIETY
卷 133, 期 19, 页码 7352-7354

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AMER CHEMICAL SOC
DOI: 10.1021/ja202605x

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  1. Ministry of Education, Culture, Sports, Science, and Technology of Japan [19105001, 21350023, 21108502]
  2. Grants-in-Aid for Scientific Research [19105001, 21350023, 21108502] Funding Source: KAKEN

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Reaction of isolable 1,1,4,4-tetrakis[bis(trimethylsilyl)methyl]-1,4-diisopropyltetrasila-2-yne (1) with an equiv amount of 4-dimethylaminopyridine unexpectedly produced the intramolecularly N-coordinated silylene 2 as the primary product. However, 2 was not thermally stable at room temperature in solution and slowly isomerized to silyl anion 3 with a zwitterionic structure via 1,2-hydrogen migration followed by Si-N bond formation.

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