title: Tris(bis(trimethylsilyl)amido)samarium: X-ray structure and DFT study.
abstract: The compound Sm[N(SiMe(3))(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(SiH(3))(SiH(2)Me)](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 beta-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-(beta-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-(beta-Si-C) chemical bonding but also illustrates the relevance of electrostatic terms in the agostic interaction. Sm-N and N-Si pi 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.
authors.affiliation: Chemistry Division, Los Alamos National Laboratory, Mail Stop J514, Los Alamos, New Mexico 87545, USA.
authors.forename: Erik D
authors.initials: ED
authors.lastname: Brady
authors.forename: David L
authors.initials: DL
authors.lastname: Clark
authors.forename: John C
authors.initials: JC
authors.lastname: Gordon
authors.forename: P Jeffrey
authors.initials: PJ
authors.lastname: Hay
authors.forename: D Webster
authors.initials: DW
authors.lastname: Keogh
authors.forename: Rinaldo
authors.initials: R
authors.lastname: Poli
authors.forename: Brian L
authors.initials: BL
authors.lastname: Scott
authors.forename: John G
authors.initials: JG
authors.lastname: Watkin