Structural and density functional studies of uranium(III) and lanthanum(III) complexes with a neutral tripodal N-donor ligand suggesting the presence of a U-N back-bonding interaction.
The crystal structures of two trisiodide octacoordinated uranium(III) complexes of tris[(2-pyrazinyl)methyl]amine (tpza), which differ only by the ligand occupying the eighth coordination site (thf or MeCN), and of their lanthanum(III) analogues have been determined. In the acetonitrile adducts the M-N(pyrazine) distances are very similar for U(III) and La(III), while the U-N(acetonitrile) distance is 0.05 A shorter than the La-N(acetonitrile) distance. In the [M(tpza)I(3)(thf)] complexes in which the monodentate acetonitrile ligand, a weak pi-acceptor ligand, is replaced by a thf molecule, a sigma-donor only, the mean value of the distance U-N(pyrazine) is 0.05 A shorter than the mean value of the La-N(pyrazine) distance. Since we are comparing isostructural compounds of ions with very similar ionic radii, these differences indicate the presence of a stronger M-N interaction in the U(III) complexes and therefore suggest the presence of a covalent contribution to the U-N bonding. The selectivity of the tpza ligand toward U(III) complexation (with respect to that of La(III)) in the presence of sigma-donor-only ligands has been quantified by the value of K(U(tpza))/K(La(tpza)) measured to be 3.3 +/- 0.5. The analysis of the metal-N-donor ligand bonding was carried out by a quasi-relativistic density functional theory study on small model compounds, of formula I(3)M-L (M = La, Nd, U; L = acetonitrile, pyrazine) and I(3)M-(pyrazine)(3) (M = La, U). The structural data obtained from geometry optimizations on these systems reproduce experimental trends, i.e., a decrease in the M-N distance from La to U, combined with an increase of the C-N distance in the acetonitrile derivatives. A detailed orbital analysis carried out on the resulting optimized complexes did not reveal any orbital interaction between the trivalent lanthanide cations (Ln(3+)) and the N-donor ligands. In contrast, a back-donation electron transfer from 5f U(3+) orbitals to the pi* virtual orbital of the ligand was observed for both acetonitrile and pyrazine. Evaluation of the total bonding energy between the MI(3) and L fragments shows that this orbital interaction leads to a stabilization of the uranium(III) system compared to the lanthanide species.
Mazzanti
Marinella
M
Laboratoire de Reconnaissance Ionique, Service de Chimie Inorganique et Biologique, UMR 5046 CEA-CNRS-Université J. Fourier Grenoble, Département de Recherche Fondamentale sur la Matière Condensée, CEA-Grenoble, France. mazzanti@drfmc.ceng.cea.fr
Wietzke
Raphaël
R
Pécaut
Jacques
J
Latour
Jean-Marc
JM
Maldivi
Pascale
P
Remy
Michael
M