Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers

Abstract: Metallacyclobutadienes (MCBDs) are key intermediates of alkyne metathesis reactions. There are in principle two isomerization pathway from kinetic to thermodynamic MCBDs, intermolecular and intramolecular. However, systems that simultaneously isolate two kinds of MCBD isomers have not been achieved, thus restricting the mechanistic studies of the isomerization. Here the reactivity of a metallapentalyne that contains an M≡C bond within the aromatic ring, with alkynes to afford a series of MCBD‐fused metallapentalenes is studied. In some cases, both kinetic and thermodynamic products are isolated in the same system, which has never been observed in previous MCBD reactions. Furthermore, the isomerization of MCBD‐fused metallapentalenes is investigated both experimentally and theoretically, indicating that it is an intramolecular process involving a metallatetrahedrane (MTd) intermediate. This research provides experimental evidence demonstrating that one MCBD can undergo intramolecular rearrangement to transform into another.

Location
Deutsche Nationalbibliothek Frankfurt am Main
Extent
Online-Ressource
Language
Englisch

Bibliographic citation
Metallacyclobutadienes: Intramolecular Rearrangement from Kinetic to Thermodynamic Isomers ; day:05 ; month:08 ; year:2024 ; extent:6
Advanced science ; (05.08.2024) (gesamt 6)

Creator
Cai, Yuanting
Hua, Yuhui
Lu, Zhengyu
Chen, Jiangxi
Chen, Dafa
Xia, Haiping

DOI
10.1002/advs.202403940
URN
urn:nbn:de:101:1-2408061427261.758141695167
Rights
Open Access; Der Zugriff auf das Objekt ist unbeschränkt möglich.
Last update
14.08.2025, 10:54 AM CEST

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Associated

  • Cai, Yuanting
  • Hua, Yuhui
  • Lu, Zhengyu
  • Chen, Jiangxi
  • Chen, Dafa
  • Xia, Haiping

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