Disilene–Silylene Interconversion: A Synthetically Accessible Acyclic Bis(silyl)silylene

Autor:	Shigeyoshi Inoue, Philipp Frisch, Amelie Porzelt, Dominik Reiter, Philipp J. Altmann, Richard Holzner
Rok vydání:	2019
Předmět:	Silylation Chemistry Silylene General Chemistry 010402 general chemistry 01 natural sciences Biochemistry Oxidative addition Catalysis 0104 chemical sciences chemistry.chemical_compound Colloid and Surface Chemistry Computational chemistry Reactivity (chemistry) Disilene
Zdroj:	Journal of the American Chemical Society. 141:13536-13546
ISSN:	1520-5126 0002-7863
Popis:	Silylenes have recently shown fascinating reactivity patterns, which are normally observed almost exclusively for transition-metal complexes. In particular, very reactive representatives are considered to be promising candidates, which may become powerful and economical alternatives for catalytic applications in the future. Here, we present the isolation of an equilibrium mixture consisting of a tetrasilyldisilene and its isomeric bis(silyl)silylene, the first isolable silylene of this type. Preliminary investigations demonstrate the extreme inherent reactivity via facile small-molecule activation even under very mild conditions. Thus, the oxidative addition of challenging targets such as H2 and NH3 was achieved. In addition, by synthesizing donor-stabilized bis(silyl)silylenes we gained further insights into the disilene-silylene rearrangement by 1,2-silyl migrations. Thorough theoretical calculations support the observed experimental results.
Databáze:	OpenAIRE
Externí odkaz:	https://explore.openaire.eu/search/publication?articleId=doi_dedup___::ec934fbf30ee887f0024d7d2b6439a7a https://doi.org/10.1021/jacs.9b05318 Zobrazit plný text záznamu