Thorium-nitrogen multiple bonds provide evidence for pushing-from-below for early actinides - INSA Toulouse - Institut National des Sciences Appliquées de Toulouse Accéder directement au contenu
Article Dans Une Revue Nature Communications Année : 2019

Thorium-nitrogen multiple bonds provide evidence for pushing-from-below for early actinides

Résumé

Although the chemistry of uranium-ligand multiple bonding is burgeoning, analogous complexes involving other actinides such as thorium remain rare and there are not yet any terminal thorium nitrides outside of cryogenic matrix isolation conditions. Here, we report evidence that reduction of a thorium-azide produces a transient Th N triple bond, but this activates C-H bonds to produce isolable parent imido derivatives or it can be trapped in an N-heterocycle amine. Computational studies on these thorium-nitrogen multiple bonds consistently evidences a sigma > pi energy ordering. This suggests pushing-from-below for thorium, where 6p-orbitals principally interact with filled f-orbitals raising the sigma-bond energy. Previously this was dismissed for thorium, being the preserve of uranium-nitrides or the uranyl dication. Recognising that pushing-from-below perhaps occurs with thorium as well as uranium, and with imido ligands as well as nitrides, suggests this phenomenon may be more widespread than previously thought.
Fichier principal
Vignette du fichier
41467_2019_Article_12206.pdf (1.89 Mo) Télécharger le fichier
Origine Fichiers éditeurs autorisés sur une archive ouverte

Dates et versions

hal-04022176 , version 1 (09-03-2023)

Licence

Identifiants

Citer

Jingzhen Du, Carlos Alvarez-Lamsfus, Elizabeth P. Wildman, Ashley J. Wooles, Laurent Maron, et al.. Thorium-nitrogen multiple bonds provide evidence for pushing-from-below for early actinides. Nature Communications, 2019, 10, ⟨10.1038/s41467-019-12206-5⟩. ⟨hal-04022176⟩
9 Consultations
12 Téléchargements

Altmetric

Partager

Gmail Mastodon Facebook X LinkedIn More