Tris(bis(trimethylsilyl)amido)samarium: X-ray Structure and DFT Study - CNRS - Centre national de la recherche scientifique Accéder directement au contenu
Article Dans Une Revue Inorganic Chemistry Année : 2003

Tris(bis(trimethylsilyl)amido)samarium: X-ray Structure and DFT Study

Résumé

The compound Sm[N(SiMe3)2]3 has been investigated experimentally by X-ray crystallography and computationally by DFT methods. The structure is analogous to that of other tris[bis(trimethylsilyl)amido]lanthanides, featuring positional disorder of the metal atom above and below the plane defined by the three N donor atoms, resulting in a trigonal pyramidal configuration. One of the methyl groups of each amido ligand is placed above the apex of the pyramid at close distance to the metal center suggesting the presence of agostic interactions. The DFT calculations have been carried out on the real molecule and on a Si[N(SiH3)(SiH2Me)]3 model where the unique Me group was placed above the apex of the pyramid to probe the agostic interaction. In both cases, the optimized geometry reproduces very well the experimental structure and indicates the presence of β-Si−C agostic interactions. A comparison of the optimized geometries obtained in the presence/absence of the Sm d and the Si d orbitals serves to illustrate the relevance of these orbitals for (i) the establishment of the pyramidal configuration at Sm, (ii) the Sm−N bond length, and (iii) the Sm−(β-Si−C) bond length. The bonding analysis, which was carried out by both Mulliken and NBO methods, not only confirms the importance of the metal d orbitals for the Sm−N and Sm−(β-Si−C) chemical bonding but also illustrates the relevance of electrostatic terms in the agostic interaction. Sm−N and N−Si π bonding is present according to the bonding analysis but is not important for enforcing the planar configuration at N, nor the pyramidal configuration at Sm.
Fichier principal
Vignette du fichier
186-10.1021-ic0341690-Accepted.pdf (914.07 Ko) Télécharger le fichier
Origine : Fichiers produits par l'(les) auteur(s)

Dates et versions

hal-03282451 , version 1 (19-07-2021)

Identifiants

Citer

Erik Brady, David Clark, John Gordon, P. Jeffrey Hay, D. Webster Keogh, et al.. Tris(bis(trimethylsilyl)amido)samarium: X-ray Structure and DFT Study. Inorganic Chemistry, 2003, 42 (21), pp.6682-6690. ⟨10.1021/ic0341690⟩. ⟨hal-03282451⟩
14 Consultations
63 Téléchargements

Altmetric

Partager

Gmail Facebook X LinkedIn More