σ-Cyclopropyl to π-Allyl Rearrangement at AuIII - Université de Pau et des Pays de l'Adour Accéder directement au contenu
Article Dans Une Revue Angewandte Chemie International Edition Année : 2023

σ-Cyclopropyl to π-Allyl Rearrangement at AuIII

Résumé

The possibility for AuIII σ-cyclopropyl complexes to undergo ring-opening and give π-allyl complexes was interrogated. The transformation was first evidenced within (P,C)-cyclometalated complexes, it occurs within hours at −50 °C. It was then generalized to other ancillary ligands. With (N,C)-cyclometalated complexes, the rearrangement occurs at room temperature while it proceeds already at −80 °C with a dicationic (P,N)-chelated complex. Density Functional Theory (DFT) calculations shed light on the mechanism of the transformation, a disrotatory electrocyclic ring-opening. Intrinsic Bond Orbital (IBO) analysis along the reaction profile shows the cleavage of the distal σ(CC) bond to give a π-bonded allyl moiety. Careful inspection of the structure and bonding of cationic σ-cyclopropyl complexes support the possible existence of C−C agostic interactions at AuIII.
Fichier principal
Vignette du fichier
Angew Chem Int Ed - 2023 - Holmsen - ‐Cyclopropyl to ‐Allyl Rearrangement at AuIII.pdf (4.47 Mo) Télécharger le fichier
Origine : Fichiers éditeurs autorisés sur une archive ouverte

Dates et versions

hal-04157609 , version 1 (11-07-2023)

Identifiants

Citer

Marte S M Holmsen, David Vesseur, Yago García‐rodeja, Karinne Miqueu, D. Bourissou. σ-Cyclopropyl to π-Allyl Rearrangement at AuIII. Angewandte Chemie International Edition, 2023, 62 (31), pp.e202305280. ⟨10.1002/anie.202305280⟩. ⟨hal-04157609⟩
47 Consultations
21 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More