475661-97-3Relevant academic research and scientific papers
The first example of μ2-imido functionality bound to a lanthanide metal center: X-ray crystal structure and DFT study of [(μ-ArN)Sm(μ-NHAr)(μ-Me)AlMe2]2 (Ar = 2,6-iPr2C6H3)
Gordon, John C.,Giesbrecht, Garth R.,Clark, David L.,Hay, P. Jeffrey,Keogh, D. Webster,Poli, Rinaldo,Scott, Brian L.,Watkin, John G.
, p. 4726 - 4734 (2002)
Reaction of 3 equiv of 2,6-diisopropylaniline with Sm[N(SiMe3)2]3 affords the dimeric species [Sm(NHAr)3]2 (1). X-ray crystallography illustrates that each metal center in 1 engages in an η6-arene interaction with the aryl ring of an amide ligand attached to an adjacent samarium. IR spectroscopy indicates that the π-arene interactions are maintained in solution. Reaction of 1 with 4 equiv of trimethylaluminum leads to formation of the bis(μ-imido) complex [(μ-ArN)Sm(μ-NHAr)(μ-Me)AlMe2]2 (2). The molecular structure of 2 contains a unique central Sm2N2 core which displays extremely short bridging Sm-N distances of 2.152-(8) and 2.271(7) A?, characteristic of an imido complex. Density functional theory (DFT) calculations have been carried out in order to gain a better understanding of the nature of the bonding interactions within complex 2 and indicate that the 5d metal acceptor orbitals play a significant role in stabilizing π-donation from the imido groups to the samarium centers within the Sm2N2 core.
